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| United States Patent |
5,077,165
|
|
Kato
, et al.
|
December 31, 1991
|
Electrophotographic lithographic printing plate precursor
Abstract
A lithographic printing plate precursor excellent in oil-desensitivity,
whereby an original is faithfully reproduced without occurrence of overall
or spotted stains as an offset master is provided, which comprises an
electrically conductive support and at least one photoconductive layer,
provided thereon, containing photoconductive zinc oxide and a binder
resin, in which said photoconductive layer contains hydrophilic resin
grains having an average grain diameter of same as or smaller than the
maximum grain diameter of said photoconductive zinc oxide grains, and said
binder resin contains at least one of Resin A having a weight average
molecular weight of 1.times.10.sup.3 to 2.times.10.sup.4 and Resin B
having a weight average molecular weight of at least 3.times.10.sup.4.
| Inventors:
|
Kato; Eiichi (Shizuoka, JP);
Ishii; Kazuo (Shizuoka, JP)
|
| Assignee:
|
Fuji Photo Film Co., Ltd. (Kanagawa, JP)
|
| Appl. No.:
|
538053 |
| Filed:
|
June 13, 1990 |
Foreign Application Priority Data
| Current U.S. Class: |
430/89; 430/49; 430/96 |
| Intern'l Class: |
G03G 005/087; G03G 005/09 |
| Field of Search: |
430/49,96,89
|
References Cited
U.S. Patent Documents
| 4929526 | May., 1990 | Kato et al. | 430/49.
|
| 4968572 | Nov., 1990 | Kato et al. | 430/96.
|
| 4971870 | Nov., 1990 | Kato et al. | 430/49.
|
| 4977049 | Dec., 1990 | Kato | 430/96.
|
| Foreign Patent Documents |
| 0307227 | Mar., 1989 | EP | 430/96.
|
Primary Examiner: Martin; Roland
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak & Seas
Claims
What is claimed is:
1. An electrophotographic lithographic printing plate precursor comprising
a conductive support having provided thereon at least one photoconductive
layer containing photoconductive zinc oxide and a binder resin, wherein
said photoconductive layer contains hydrophilic resin grains having an
average grain diameter the same as or smaller than the maximum grain
diameter of said photoconductive zinc oxide grains and said binder resin
comprises at least one of the following Resin A and at least one of the
following Resin B:
(a) Resin A: a resin having a weight average molecular weight of
1.times.10.sup.3 to 2.times.10.sup.4, containing at least 30% by weight of
recurring units represented by the following formula (I) as polymeric
components and having at least one polar group bonded to one end of the
polymer main chain, selected from the group consisting of --PO.sub.3
H.sub.2, --SO.sub.3 H, --COOH, --OH.
##STR138##
wherein R.sub.0 is a hydrocarbon group or --OR.sub.0 ', wherein R.sub.0 '
represents a hydrocarbon group, and R.sub.0 further representing cyclic
acid anhydride-containing groups:
##STR139##
in which a.sub.1 and a.sub.2 each, individually, represents a hydrogen
atom, halogen atoms, a cyano group and hydrocarbon groups and R.sub.1
represents a hydrocarbon group; and
(b) Resin B: a resin consisting of a copolymer having a weight average
molecular weight of at least 3.times.10.sup.4 and obtained from a
monofunctional macromonomer and a monomer, said monofunctional
macromonomer having a polymerizable double bond group represented by the
following formula (IIc) bonded to only one end of a polymer main chain
containing at least one of recurring units represented by the following
formulae (IIa) and (IIb) as polymeric components and having a weight
average molecular weight of at most 2.times.10.sup.4 and said monomer
represented by the following formula (III):
##STR140##
in which X.sub.0 represents --COO--, --OCO--, --(CH.sub.2).sub.1 --OCO--,
--(CH.sub.2).sub.1 --COO--, --O--, --CONHCOO--, --CONHCONH--, --SO.sub.2
--, --CO--,
##STR141##
wherein R.sub.2 represents a hydrogen atom or a hydrocarbon group or
##STR142##
l being an integer of 1 to 3. Q.sub.0 represents an aliphatic group
containing 1 to 18 carbon atoms or an aromatic group containing 6 to 12
carbon atoms and a.sub.3 and a.sub.4 each, individually has the same
meaning as a.sub.1 and a.sub.2 :
##STR143##
in which Q.sub.1 represents --CN, --CONH.sub.2 or
##STR144##
Y represents a hydrogen atom, a halogen atom, an alkoxy group or
--COOZ.sub.0, wherein Z.sub.0 represents an alkyl group, an aralkyl group
or an aryl group, and a.sub.5 and a.sub.6 each, individually, has the same
meaning as a.sub.1 and a.sub.2 of formula (I);
##STR145##
in which V represents the same meaning as X.sub.0 in formula (IIa),
b.sub.1 and b.sub.2 each, individually, represents a hydrogen atom,
halogen atoms, a cyano group, hydrocarbon groups, --COOR.sub.3 or
--COOR.sub.3 via hydrocarbon groups, wherein R.sub.3 represents a hydrogen
atom or an optionally substituted hydrocarbon group:
##STR146##
in which X.sub.1 has the same meaning as X.sub.0 in formula (IIa) or V in
formula (IIc), Q.sub.2 has the same meaning as Q.sub.0 in formula (IIa)
and a.sub.7 and a.sub.8 each, individually, has the same meaning as
a.sub.1 and a.sub.2 in formula (I).
2. A electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the recurring unit represented by formula (I) of Resin
A is an aryl group-containing methacrylate component represented by at
least one of formulae (la) and (Ib) as described below:
##STR147##
in which T.sub.1 and T.sub.2 each represents independently a hydrogen
atom, hydrocarbon groups containing 1 to 10 carbon atoms, a chlorine atom,
a bromine atom, --COR.sub.4 or --COOR.sub.4, wherein R.sub.4 represents a
hydrocarbon group containing 1 to 10 carbon atoms, both T.sub.1 and
T.sub.2 not being hydrogen atom at the same time, and L.sub.1 and L.sub.2
each represents direct bonds for bonding --COO-- and benzene ring or
bonding groups containing 1 to 4 bonding atoms.
3. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein Resin B is a resin having at least one polar group
selected from the group consisting of --PO.sub.3 H.sub.2, --SO.sub.3 H,
--COOH, --OH, --SH,
##STR148##
wherein R.sub.5 represents a hydrocarbon group or --OR.sub.5 ', wherein
R.sub.5 ' represents a hydrocarbon group, R.sub.5 further representing
cyclic acid anhydride-containing groups, --CHO, --CONH.sub.2, --SO.sub.2
NH.sub.2 and
##STR149##
wherein R.sub.6 and R.sub.7 each, individually, represents a hydrogen atom
or hydrocarbon groups, bonded to only one end of at least one polymer main
chain.
4. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the hydrophilic resin has a high order network
structure.
5. An electrophotographic lithographic printing plate precursor as claimed
in claim 4, wherein the high order network structure is formed by
cross-linking the polymer molecule chains of a polymer comprising
hydrophilic polymeric components.
6. An electrophotographic lithographic printing plate precursor as claimed
in claim 5, wherein the cross-linking is carried out by the use of a
cross-linking agent or hardening agent.
7. An electrophotographic lithographic printing plate precursor as claimed
in claim 5, wherein the cross-linking is carried out by polymerizing a
monomer corresponding to the hydrophilic polymeric component in the
presence of a multi-functional monomer or oligomer containing at least two
polymerizable functional groups.
8. An electrophotographic lithographic printing plate precursor as claimed
in claim 5, wherein the cross-linking is carried out by polymerizing or
high molecular reaction of a polymer having reactive groups with the
hydrophilic polymerizable component.
9. An electrophotographic lithographic printing plate precursor as claimed
in claim 4, wherein the hydrophilic resin has a solubility of at most 80%
by weight in water.
10. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the hydrophilic resin grains have a maximum grain
diameter of at most 10 .mu.m and an average grain diameter of at most 1
.mu.m.
11. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the hydrophilic resin grains are in a proportion of
0.1 to 5 parts by weight to 100 parts by weight of the photoconductive
zinc oxide.
12. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the hydrophilic resin is selected from the group
consisting of synthetic hydrophilic resins and natural hydrophilic resins.
13. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the hydrophilic resin consists of a homopolymer or
copolymer comprising a polymeric component having at least one hydrophilic
group in the polymer side chain, the polymeric component being in a
proportion of 20 to 100% by weight to the resin.
14. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein Resins A and B are used in a Resin A to Resin B ratio
of 5 to 80 to 95 to 20 by weight.
15. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the binder resin is in a proportion of 10 to 100 parts
by weight to 100 parts by weight of the photoconductive zinc oxide.
16. An electrophotographic lithographic printing plate precursor as claimed
in claim 1, wherein the photoconductive layer further contains at least
one dye as a spectral sensitizer.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an electrophotographic lithographic printing
plate precursor made by an electrophotographic system and more
particularly, it is concerned with an improvement in a photoconductive
layer forming composition for the lithographic printing plate precursor.
2. Description of the Prior Art
A number of offset masters for directly producing printing plates have
hitherto been proposed and some of them have already been put into
practical use. Widely employed among them is a system in which a
photoreceptor comprising a conductive support having provided thereon a
photoconductive layer mainly comprising photoconductive particles, for
example, of zinc oxide and a resin binder is subjected to an ordinary
electrophotographic processing to form a highly lipophilic toner image on
the surface of the photoreceptor, followed by treating the surface with an
oil-desensitizing solution referred to as an etching solution to
selectively render non-image areas hydrophilic and thus obtain an offset
printing plate.
Requirements of offset masters for obtaining satisfactory prints include:
(1) an original should be reproduced faithfully on the photoreceptor; (2)
the surface of the photoreceptor has affinity with an oil-desensitizing
solution so as to render non-image areas sufficiently hydrophilic, but, at
the same time, has resistance to solubilization; and (3) a photoconductive
layer having an image formed thereon is not released during printing and
is well receptive to dampening water so that the non-image areas retain
the hydrophilic properties sufficiently to be free from stains even upon
printing a large number of prints.
It is known that these properties are affected by the ratio of zinc oxide
to a resin binder in the photoconductive layer. For example, if the ratio
of a binder resin to zinc oxide particles is decreased, oil-desensitivity
of the surface of the photoconductive layer is increased to reduce
background stains, but, on the other hand, the internal cohesion of the
photoconductive layer per se is weakened, resulting in reduction of
printing durability due to insufficient mechanical strength. If the ratio
of a binder resin to zinc oxide particles is increased, on the other hand,
printing durability is improved, but background staining becomes
conspicuous. It is a matter of course that the background staining is a
phenomenon associated with the degree of oil-desensitization achieved and
it has been made apparent that the oil-desensitization of the
photoconductive layer surface depends on not only the binder resin/zinc
oxide ratio in the photoconductive layer, but also the kind of the binder
resin used to a great extent.
For particular use as an offset master, occurrence of background stains due
to insufficient oil-desensitivity presents a serious problem. In order to
solve this problem, various resins for binding zinc oxide have been
proposed to improve the oil-desensitization, including resins of weight
average molecular weight (Mw) 1.8-10.times.10.sup.-4 and glass transition
point (Tg) 10.degree.-80.degree. C. obtained by copolymerizing
(meth)acrylate monomers and other monomers in the presence of fumaric acid
in combination with copolymers of (meth)acrylate monomers and other
monomers than fumaric acid, as disclosed in Japanese Patent Publication
No. 31011/1975; terpolymers each containing a (meth)acrylic acid ester
unit having a substituent having carboxylic acid group at least 7 atoms
distant from the ester linkage, as disclosed in Japanese Patent Laid-Open
Publication No. 54027/1978; tetra- or pentamers each containing an acrylic
acid unit and hydroxyethyl (meth)acrylate unit, as disclosed in Japanese
Patent Laid-Open Publication Nos. 20735/1979 and 202544/1982; terpolymers
each containing a (meth)acrylic acid ester unit having an alkyl group
having 6 to 12 carbon atoms as a substituent and a vinyl monomer
containing carboxylic acid group, as disclosed in Japanese Patent
Laid-Open Publication No. 046/1983; and the like. These resins function to
improve the oil-desensitivity of photoconductive layers.
Nevertheless, evaluation of such resins as noted above for improving the
oil-desensitization indicate that none of them is completely satisfactory
in terms of stain resistance, printing durability and the like.
Furthermore, it has hitherto been studied to use resins having functional
groups capable of forming hydrophilic groups through decomposition as such
a binder resin, for example, those having functional groups capable of
forming hydroxyl groups as disclosed in Japanese Patent Laid-Open
Publication Nos. 195684/1987, 210475/1987 and 210476/1987 and those having
functional groups capable of forming carboxyl groups as disclosed in
Japanese Patent Laid-Open Publication No. 12669/1987.
These resins are those which form hydrophilic groups through hydrolysis or
hydrogenolysis with an oil-desensitizing solution or dampening water used
during printing. When using them as a binder resin for a lithographic
printing plate precursor, it is possible to avoid various problems, e.g.,
deterioration of smoothness, deterioration of electrophotographic
properties such as dark charge retention and photosensitivity, etc., which
are considered to be caused by strong interaction of the hydrophilic
groups and surfaces of photoconductive zinc oxide particles in the case of
using resins intrinsically having hydrophilic groups per se, and at the
same time, a number of prints with clear image quality and without
background stains can be obtained, since the hydrophilic property of
non-image areas rendered hydrophilic with an oil-desensitizing solution is
further increased by the above described hydrophilic groups formed through
decomposition in the resin to make clear the lipophilic property of image
areas and the hydrophilic property of non-image areas and to prevent the
non-image areas from adhesion of a printing ink during printing.
At the present time, in the electrophotographic lithographic printing, a
higher efficiency has been required and in particular, it has been
required to increase the speeds of plate making and etching and to obtain
a print with a clear image quality, particularly free from background
stains, from the start of printing, thus reducing loss of prints.
In the scanning exposing system using a semiconductor laser beam,
furthermore, higher performances are required for static properties, in
particular, dark charge retension and photosensitivity, since the exposing
time is longer and the exposing intensity is more restricted than in the
overall and simultaneously exposing system of the prior art using visible
rays.
For such requirements is insufficient the above proposed offset printing
plate using the binder resin capable of forming hydrophilic groups through
decomposition with respect to the problems of increasing the etching speed
and reducing the loss of prints.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an electrophotographic
lithographic printing plate precursor, whereby the disadvantages of the
prior art, as described above, can be overcome.
It is another object of the present invention to provide a lithographic
printing plate precursor excellent in oil-desensitivity, as well as static
properties, in particular, dark charge retention and photosensitivity,
whereby an original is faithfully reproduced without occurrence of overall
or spotted stains as an offset master.
It is a further object of the present invention to provide a lithographic
printing plate with a clear and good quality image even if the ambient
conditions during forming a reproduced image are fluctuated from low
temperature and low humidity to high temperature and high humidity.
It is a still further object of the present invention to provide a
lithographic printing plate precursor with a high printing durability,
high printing durability, in which the hydrophilic property of non-image
areas is sufficiently held to prevent occurrence of background stains even
if the steps of from etching to printing are speeded up.
It is a still further object of the present invention to provide a CPC
photoreceptor with excellent static properties and small dependence on the
ambient conditions.
It is a still further object of the present invention to provide a
lithographic printing plate precursor which is hardly affected by the kind
of sensitizing dyes to be jointly used.
These objects can be attained by an electrophotographic lithographic
printing plate precursor comprising a conductive support and at least one
photoconductive layer, provided thereon, containing photoconductive zinc
oxide and a binder resin, wherein said photoconductive layer contains
hydrophilic resin grains having an average grain diameter of same as or
smaller than the maximum grain diameter of said photoconductive zinc oxide
grains and said binder resin contains at least one of the following Resin
A and Resin B:
Resin A
A resin having a weight average molecular weight of 1.times.10.sup.3 to
2.times.10.sup.4, containing at least 30% by weight of recurring units
represented by the following general formula (I) as polymeric components
and having at least one polar group bonded to one end of the polymer main
chain, selected from the group consisting of --PO.sub.3 H.sub.2,
--SO.sub.3 H, --COOH, --OH,
##STR1##
wherein R.sub.0 is a hydrocarbon group or --OR.sub.0 ' (R.sub.0 ':
hydrocarbon group) and cyclic acid anhydride-containing groups:
General Formula (I)
##STR2##
in which a.sub.1 and a.sub.2 each represent, same or different, hydrogen
atom, halogen atoms, cyano group and hydrocarbon groups and R.sub.1
represents a hydrocarbon group.
Resin B
A resin consisting of a copolymer having a weight average molecular weight
of at least 3.times.10.sup.4 and obtained from a monofunctional
macromonomer having a polymerizable double bond group represented by the
following general formula (IIc), bonded to only one end of a polymer main
chain containing at least one of recurring units represented by the
following general formulae (IIa) and (IIb) as polymeric components and
having a weight average molecular weight of at most 2.times.10.sup.4 and a
monomer represented by the following general formula (III):
General Formula (IIa)
##STR3##
in which X.sub.0 represents --COO--, --OCO--, --(CH.sub.2).sub.1 --OCO--,
--(CH.sub.2).sub.1 --COO--, --O--, --CONHCOO--, --CONHCONH--, --SO.sub.2
--, --CO--,
##STR4##
wherein R.sub.2 represents hydrogen atom or hydrocarbon group or
##STR5##
l being an integer of 1 to 3, Q.sub.0 represents an aliphatic group
containing 1 to 18 carbon atoms or an aromatic group containing 6 to 12
carbon atoms and a.sub.3 and a.sub.4 each have, same or different, the
same meanings as a.sub.1 and a.sub.2.
General Formula (IIb)
##STR6##
in which Q.sub.1 represents --CN, --CONH.sub.2 or
##STR7##
Y represents hydrogen atom, halogen atom, alkoxy group or --COOZ.sub.0
wherein Z.sub.0 represents an alkyl group, aralkyl group or aryl group,
and a.sub.5 and a.sub.6 each have, same or different, the same meanings as
a.sub.1 and a.sub.2 of General Formula (I).
General Formula (IIc)
##STR8##
in which V represents the same meaning as X.sub.0 in General Formula
(II.sub.a), b.sub.1 and b.sub.2 each represents, same or different,
hydrogen atom, halogen atoms, cyano group, hydrocarbon groups,
--COOR.sub.3 or --COOR.sub.3 via hydrocarbon groups wherein R.sub.3
represents hydrogen atom or an optionally substituted hydrocarbon group.
General Formula (III)
##STR9##
in which X.sub.1 has the same meaning as X.sub.0 in General Formula (IIa)
or V in General Formula (IIc), Q.sub.2 has the same meaning as Q.sub.0 in
General Formula (IIa) and a.sub.7 and a.sub.8 each have, same or
different, the same meanings as a.sub.1 and a.sub.2 in General Formula (I)
.
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the above described Resin A may contain, as the
recurring unit represented by General Formula (I), aryl group-containing
methacrylate components represented by the following General Formulae (Ia)
and/or (Ib).
General Formula (Ia)
##STR10##
General Formula (Ib)
##STR11##
in which T.sub.1 and T.sub.2 each represent independently hydrogen atom,
hydrocarbon groups containing 1 to 10 carbon atoms, chlorine atom, bromine
atom, --COR.sub.4 or --COOR.sub.4 wherein R.sub.4 represents a hydrocarbon
group containing 1 to 10 carbon atoms, T.sub.1 and T.sub.2 being not
hydrogen atom at the same time, and L.sub.1 and L.sub.2 each represents
direct bonds for bonding --COO-- and benzene ring or bonding groups
containing 1 to 4 bonding atoms.
In the present invention, the above described Resin B may be a resin
consisting of a copolymer obtained from at least a monofunctional
macromonomer having a polymerizable double bond group represented by
General Formula (IIc), bonded to only one end of a polymer main chain
containing at least one of polymeric components represented by General
Formulae (IIa) and (IIb) and having a weight average molecular weight of
at most 2.times.10.sup.4 and a monomer represented by General Formula
(III), and having at least one polar group selected from the group
consisting of --PO.sub.3 H.sub.2, --SO.sub.3 H, --COOH, --OH, --SH,
##STR12##
wherein R.sub.5 represents a hydrocarbon group or --OR.sub.5 ' (R.sub.5 '
represents a hydrocarbon group), cyclic acid anhydride-containing groups,
--CHO, --CONH.sub.2, --SO.sub.2 NH.sub.2 and
##STR13##
wherein R.sub.6 and R.sub.7 each represents, same or different, hydrogen
atom or hydrocarbon groups, bonded to only one end of at least one polymer
main chain.
The hydrophilic resin used in the present invention includes resins such as
having a higher order network structure and such that the grain has the
above described average grain diameter and the film formed by dissolving
the resin grains in a suitable solvent and then coating has a contact
angle with distilled water of 50 degrees or less, preferably 30 degrees or
less, measured by a goniometer.
In the present invention, it is important that the hydrophilic resin is
dispersed in the photoconductive layer in the form of grains whose average
grain diameter is same as or smaller than the maximum grain diameter of
the photoconductive zinc oxide grains. Such hydrophilic resin grains have
such smaller specific areas and less interaction with zinc oxide grain
surfaces than those present under molecular state that a lithographic
printing plate can be given capable of exhibiting good printing properties
because of less deterioration of electrophotographic properties. If there
are resin grains having larger grain diameters than zinc oxide grains, the
electrophotographic properties are deteriorated and in particular, uniform
electrification cannot be obtained, thus resulting in density unevenness
in an image area, disappearance of letters or fine lines and background
staining in a non-image area in a reproduced image.
Specifically, the resin grains of the present invention have a maximum
grain diameter of at most 10 .mu.m, preferably at most 5 .mu.m and an
average grain diameter of at most 1.0 .mu.m, preferably at most 0.5 .mu.m.
The specific surface areas of the hydrophilic resin grains are increased
with the decrease of the grain diameter, resulting in good
electrophotographic properties, and the grain size of colloidal grains,
i.e., about 0.01 .mu.m or smaller is sufficient. However, very small
grains cause the similar troubles to those in the case of molecular
dispersion and accordingly a grain size of 0.001 .mu.m or larger is
preferable. On the other hand, zinc oxide has generally a grain diameter
of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m.
In the present invention, the hydrophilic resin grains having a high order
network structure do not meet with dissolving-out with damping water
during printing so that good printing properties can be maintained even
after a number of prints are obtained.
In the present invention, the hydrophilic resin grains having no such a
high order network structure (which will hereinafter be referred to as
simply "hydrophilic resin grains") or the hydrophilic resin grains having
a high order network structure (which will hereinafter be referred to as
simply "network hydrophilic resin grains") are preferably used in a
proportion of 0.1 to 20% by weight to 100 parts by weight of
photoconductive zinc oxide, since if the hydrophilic resin grains or
network hydrophilic resin grains are less than 0.1% by weight, the
hydrophilic property of a non-image area does not become sufficient, while
if more than 20% by weight, the hydrophilic property of a non-image area
is further improved, but electrophotographic properties and reproduced
images are deteriorated.
As the hydrophilic resin of the present invention, optionally having a
higher order network structure, there can favorably be used any of
synthetic and natural hydrophilic resins, for example, described in P.
Molyneax "Water-Soluble Synthetic Polymers: Properties and Behavior" Vol.
I and Vol. II, CRC Press Inc. (1982); C. A. Finch "Chemistry and
Technology of Water-Soluble Polymers" Plenam Press (1983); Matao Nakamura
"Water-Soluble Polymers (Suiyosei Kobunshi)" Kagaku Kogyo-sha (1973);
Kaimen Kagaku Kenkyukai "New Processing and Modifying Technique and
Development of Uses of Water-Soluble Polymers Aqueous Dispersion Type
Resins" Keiei Kaihatsu Center Shuppan-bu (1981) and Davidson
"Water-Soluble Resin" Reinhold (1968).
The synthetic hydrophilic resins include those containing, in the molecular
structures, at least one hydrophilic group selected from the group
consisting of ether group, ethylene oxide group, --OH, --SH, --COOH,
--SO.sub.2 H, --SO.sub.3 H, --PO.sub.3 H.sub.2, --CN, --CONH.sub.2, --CHO,
--SO.sub.2 R.sub.8,
##STR14##
4- to 6-membered heterocyclic ring optionally containing at least one
nitrogen atom and organosilane group.
In the above described hydrophilic groups, R.sub.8 is a hydrocarbon group
containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which can
be substituted, for example, methyl, ethyl, propyl, butyl, 2-chloroethyl,
2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl,
2-methoxybutyl, benzyl, phenyl, propenyl, methoxymethyl, ethoxymethyl and
2-methoxyethyl groups.
R.sub.9 is an aliphatic group containing 1 to 6 carbon atoms, preferably 1
to 4 carbon atoms, which can be substituted, i.e., the similar group to
R.sub.8 or --OR.sub.9 ' wherein R.sub.9 ' has the same meaning as R.sub.8.
R.sub.10 and R.sub.11 being same or different represent hydrogen atoms or
hydrocarbon groups containing 1 to 6 carbon atoms, preferably 1 to 4
carbon atoms, which can be substituted, i.e., have the same meaning as
R.sub.8. The sum of carbon atoms in R.sub.10 and R.sub.11 are at most 8,
preferably at most 6.
R.sub.12, R.sub.13 and R.sub.14 have the same meanings as R.sub.10 and
R.sub.11, which can be same or different.
X.sup..crclbar. is an anion, for example, halide ion such as chloride ion,
bromide ion or iodide ion, perchlorate ion, tetrafluoroborate ion,
hydroxide ion, carboxylate ion such as acetonate ion or propionate ion,
sulfonate ion such as methanesulfonate ion, benzenesulfonate ion or
p-toluenesulfonate ion, or the like.
.gamma. is 1 or 2 and when .gamma.=1, R.sub.12 to R.sub.14 contain at least
one acidic group such as --SO.sub.3 H, --PO.sub.3 H.sub.2 or --COOH as a
substituent. A typical example is
##STR15##
Each of the above described groups, --COOH, --SO.sub.2 H, --SO.sub.3 H,
--PO.sub.3 H.sub.2, and
##STR16##
can form a salt with an alkali metal such as lithium, sodium or potassium,
alkaline earth metal such as calcium or magnesium, or other metals such as
zinc and aluminum, or an organic base such as triethylamine, pyridine,
morpholine or piperazine.
Examples of the 4- to 6-membered heterocyclic ring optionally containing at
least one nitrogen atom, as described above, are pyridine ring, piperidine
ring, pyrrole ring, imidazole ring, pyrazine ring, pyrrolidine ring,
pyrroline ring, imidazoline ring, pyrazolidine ring, piperazine ring,
morpholine ring, pyrrolidone ring and the like. These heterocyclic rings
can be substituted by substituents, illustrative of which are halogen
atoms such as fluorine, chlorine and bromine atoms; optionally substituted
hydrocarbon groups containing 1 to 8 carbon atoms, which can be
substituted, such as methyl, ethyl, propyl, butyl, 2-chloroethyl,
2-bromoethyl, 2-hydroxyethyl, 2-cyanoethyl, 2-methoxyethyl, 2-ethoxyethyl,
2-butoxyethyl, 2-carboxyethyl, carboxymethyl, 3-sulfopropyl, 4-sulfobutyl,
2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-methanesulfonylethyl,
benzyl, carboxybenzyl, carboxymethylbenzyl, phenyl, carboxyphenyl,
sulfophenyl, methanesulfonylphenyl, ethanesulfonylphenyl,
carboxymethylphenyl, methoxyphenyl, chlorophenyl groups and the like;
--OR.sub.15 groups wherein R.sub.15 represents the above described
hydrocarbon groups containing 1 to 8 carbon atoms, which can be
substituted and --COOR.sub.16 groups wherein R.sub.16 has the same meaning
as R.sub.15.
The organosilane group includes, for example, a recurring unit represented
by the following general formula (IV):
##STR17##
wherein J is an alkyl group containing 1 to 4 carbon atoms, which can be
substituted, such as methyl, ethyl, propyl, butyl, 2-chloroethyl,
2-methoxyethyl, 2-cyanoethyl groups and the like; --OR.sub.17 group
wherein R.sub.17 has the same meaning as J or --"Z.sub.1 " group wherein
Z.sub.1 is trimethylsiloxy, pentamethyldisiloxanyl,
heptamethyltrisiloxanyl, nonamethyltetrasiloxanyl,
bis(trimethylsiloxy)methylsiloxanyl, tris(trimethylsiloxy) siloxanyl group
or the like, and K is an alkyl group containing 1 to 6 carbon atoms, which
can be substituted, such as methyl, ethyl, propyl, butyl, hexyl,
2-methoxyethyl, 2-ethoxypropyl, 2-cyanoethyl, 2-hydroxyethyl,
2-hydroxy-3-chloropropyl or 2-chloroethyl group, --OR.sub.18 group wherein
R.sub.18 has the same meaning as R.sub.17 or a group such that an
unsaturated bond selected from the group consisting of vinyl,
methacryloxy, acryloxy, methacrylamide, acrylamide, styryl and allyl
groups is polymerized and combined with another recurring unit through a
divalent hydrocarbon group containing 1 to 6 carbon atoms, and m.sub.1 and
m.sub.2 each is 0 or an integer of 1 to 10, the sum of m.sub.1 +m.sub.2
being at least 2.
The hydrophilic resin of the present invention is a homopolymer or
copolymer comprising a polymeric component having at least one of the
hydrophilic groups in the polymer side chain, the polymeric component
being in a proportion of 20 to 100% by weight, preferably 30 to 100% by
weight to the resin.
More specifically, this hydrophilic group-containing polymeric component is
represented, for example, by the following general formula (V): R1 ?
##STR18##
In the general formula (V), X.sub.2 is a direct bond or --COO--, --OCO--,
--O--, --SO.sub.2 --,
##STR19##
--CONHCOO--, --CONHCONH--,
##STR20##
wherein R.sub.19 represents hydrogen atom or optionally substituted
hydrocarbon groups containing 1 to 7 carbon atoms such as methyl, ethyl,
propyl, butyl, 2-chloroethyl, 2-hydroxyethyl, 3-bromo-2-hydroxypropyl,
2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 3-sulfopropyl, benzyl,
sulfobenzyl, methoxybenzyl, carboxybenzyl, phenyl, sulfophenyl,
carboxyphenyl, hydroxyphenyl, 2-methoxyethyl, 3-methoxypropyl,
2-methanesulfonylethyl, 2-cyanoethyl, N,N-(dichloroethyl)aminobenzyl,
N,N-(dihydroxyethyl)aminobenzyl, chlorobenzyl, methylbenzyl,
N,N-(dihydroxyethyl) aminophenyl, methanesulfonylphenyl, cyanophenyl,
dicyanophenyl, acetylphenyl groups and the like, R.sub.20 and R.sub.21
each represent, same or different, hydrogen atom, halogen atoms such as
fluorine, chlorine, and bromine atoms and aliphatic groups containing 1 to
4 carbon atoms, in particular, alkyl groups such as methyl, ethyl, propyl
and butyl groups, and i represents an integer of 1 to 6.
W is the foregoing hydrophilic group, i.e., ether group, ethylene oxide
group, --OH, --SH, --CHO, --CN, --COOH, --SO.sub.2 H, --SO.sub.3 H,
--PO.sub.3 H.sub.2, --CONH.sub.2, --SO.sub.2 R.sub.8,
##STR21##
4- to 6-membered heterocyclic rings optionally containing at least one
nitrogen atom or organosilane group, wherein R.sub.8 to R.sub.14 have the
same meaning as the foregoing R.sub.8 to R.sub.14.
L.sub.3 is a linking group selected from the group consisting of
##STR22##
--COO--, --OCO--, --O--, --S--, --SO.sub.2 --,
##STR23##
or a bonding group formed by combination of these linking groups, wherein
l.sub.1 to l.sub.4 represent, same or different, hydrogen atom, halogen
atoms such as fluorine, chlorine and bromine atoms, hydrocarbon groups
containing 1 to 7 carbon atoms which can be substituted, such as methyl,
ethyl, propyl, butyl, 2-chloroethyl, 2-methoxyethyl,
2-methoxycarbonylethyl, benzyl, methoxybenzyl, phenyl, methoxyphenyl,
methoxycarbonylphenyl groups and the like and --(L.sub.3 --W) groups in
the general formula (V), and l.sub.5 to l.sub.9 have the same meaning as
R.sub.19.
In the general formula (V), a.sub.9 and a.sub.10 represent, same or
different, hydrogen atom, halogen atoms such as fluorine, chlorine and
bromine atoms, --COOH, --COOR.sub.22 and --CH.sub.2 COOR.sub.22 wherein
R.sub.22 represents a hydrocarbon group containing 1 to 7 carbon atoms, in
particular, the same hydrocarbon groups as in R.sub.19, and alkyl groups
containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl
groups.
Examples of the above described hydrophilic group-containing polymeric
component are given below without limiting the scope of the present
invention:
##STR24##
As other polymeric components which can be copolymerized with the above
described hydrophilic group-containing polymeric components, for example,
there can be used those represented by the following general formula (Ia)
and/or (Ib).
Natural hydrophilic resins are described in detail in the foregoing
comprehensive technical materials of water-soluble high molecular water
dispersion type resins (Keiei Kaihatsu Center Shuppan-bu), for example,
lignin, glucose starch, pullulan, cellulose, alginic acid, dextran,
dextrin, gum guar, gum arabic, glycogen, lamiran, lichenin, nigeran and
derivatives thereof. As these derivatives, there can be used preferably
sulfonated, carboxylated, phosphated, sulfoalkylated, carboxyalkylated,
alkylphosphated ones and salts thereof. Two or more natural hydrophilic
resins can be used.
Among the natural hydrophilic resins, glucose polymers and derivatives are
preferable and above all, starch, glycogen, cellulose, lichenin, dextran
and nigeran are more preferable. In particular, dextran and derivatives
thereof are most preferable.
Production of fine grains or particles of the above described synthetic or
natural hydrophilic resin having a specified grain diameter can be carried
out by employing a dry or wet method well known in the art, for example,
(a) a method comprising directly pulverizing the hydrophilic resin powder
by a pulverizing mill of the prior art, such as ball mill, paint shaker,
jet mill, hammer mill, etc. and thus obtaining fine grains and (b) a
method of obtaining high molecular latex grains. The latter method of
obtaining high molecular latex grains can be carried out according to the
prior art method for producing latex grains of paints or liquid developers
for electrophotography. That is, this method comprises dispersing the
hydrophilic resin by the joint use of a dispersing polymer, more
specifically previously mixing the hydrophilic resin and dispersion aid
polymer or coating polymer, followed by pulverizing, and then dispersing
the pulverized mixture in the presence of the dispersing polymer.
For example, these methods are described in "Flowing and Pigment Dispersion
of Paints" translated by Kenji Ueki and published by Kyoritsu Shuppan
(1971), Solomon "Chemistry of Paints", "Paint and Surface Coating Theory
and Practice", Yuji Harasaki "Coating Engineering (Coating Kogaku)"
published by Asakura Shoten (1971), Yuji Harasaki "Fundamental Science of
Coating (Kiso Kagaku of Coating)" by Maki Shoten (1977) and Japanese
Patent Laid-Open Publication Nos. 96954/1987, 115171/1987 and 75651/1987.
Furthermore, the prior art method of obtaining readily latex grains or
particles by suspension polymerization or dispersion polymerization can
also be used in the present invention, for example, as described in Soichi
Muroi "Chemistry of High Molecular Latex (Kobunshi Latex no Kagaku)"
published by Kobunshi Kankokai (1970), Taira Okuda and Hiroshi Inagaki
"Synthetic Resin Emulsions (Gosei Jushi Emulsion)" published by Kobunshi
Kankokai (1978), Soichi Muroi "Introduction to High Molecular Latexes
(Kobunshi Latex Nyumon)" published by Kobunsha (1983).
In the present invention, it is preferable to use a method of obtaining
high molecular latex grains, whereby resin grains with an average grain
diameter of at most 1.0 .mu.m can readily be obtained.
In the electrophotographic lithographic printing plate precursor of the
present invention, formation of a photoconductive layer can be carried out
by any of methods of dispersing photoconductive zinc oxide in an aqueous
system, for example, described in Japanese Patent Publication Nos.
450/1976, 18599/1972 and 41350/1971 and methods of dispersing in a
non-aqueous solvent system, for example, described in Japanese Patent
Publication No. 31011/1975 and Japanese Patent Laid-Open Publication Nos.
54027/1978, 20735/1979, 202544/1982 and 68046/1983. If water remains in
the photoconductive layer, however, the electrophotographic property is
deteriorated, and accordingly, the latter methods using a non-aqueous
solvent system is preferable. Therefore, in order to adequately disperse
the hydrophilic resin latex grains of the present invention in the
photoconductive layer dispersed in a non-aqueous system, the latex grains
are preferably non-aqueous system latex grains.
As the non-aqueous solvent for the non-aqueous system latex, there can be
used any of organic solvents having a boiling point of at most 200.degree.
C., individually or in combination. Useful examples of the organic solvent
are alcohols such as methanol, ethanol, propanol, butanol, fluorinated
alcohols and benzyl alcohol, ketones such as acetone, methyl ethyl ketone,
cyclohexanone and diethyl ketone, ethers such as diethyl ether,
tetrahydrofuran and dioxane, carboxylic acid esters such as methyl
acetate, ethyl acetate, butyl acetate and methyl propionate, aliphatic
hydrocarbons containing 6 to 14 carbon atoms such as hexane, octane,
decane, dodecane, tridecane, cyclohexane and cyclooctane, aromatic
hydrocarbons such as benzene, toluene, xylene and chlorobenzene and
halogenated hydrocarbons such as methylene chloride, dichloroethane,
tetrachloroethane, chloroform, methylchloroform, dichloropropane and
trichloroethane.
When a high molecular latex is synthesized by the dispersion polymerization
method in a non-aqueous solvent system, the average grain diameter of the
latex grains can readily be adjusted to at most 1 .mu.m while
simultaneously obtaining grains of monodisperse system with a very narrow
distribution of grain diameters. Such a method is described in, for
example, K. E. J. Barrett "Dispersion Polymerization in Organic Media"
John Wiley & Sons (1975), Koichiro Murata "Polymer Processings (Kobunshi
Kako)" 23, 20 (1974), Tsunetaka Matsumoto and Toyokichi Tange "Journal of
Japan Adhesive Association (Nippon Setchaku Kyokaishi)" 9, 183 (1973),
Toyokichi Tange "Journal of Japan Adhesive Association" 23, 26 (1987), D.
J. Walbridge "NATO. Adv. Study Inst. Ser. E." No. 67, 40 (1983), British
Patent No.s 893,429 and 934,038 and U.S. Pat. Nos. 1,122,397, 3,900,412
and 4,606,989, and Japanese Patent Laid-Open Publication Nos. 179751/1985
and 185963/1985.
Specifically, the network hydrophilic resin grains consist of a homopolymer
or copolymer containing polymeric components containing in the polymer
side chain at least one of the specific hydrophilic group-containing
components, specifically described above, in at least one structure of the
recurring units of the polymer and as in the case of the foregoing
hydrophilic resins, the said polymeric components are contained as the
polymeric components of the resin in a proportion of 20 to 100% by weight,
preferably 30 to 100% by weight.
The specific general formulae and component examples of this network
hydrophilic resin are substantially the same as the general formulae (IV)
and (V) and component examples (a-1) to (a-57) of the foregoing
hydrophilic resins.
Examples of the network natural hydrophilic resin are described in detail
in Kaimen Kagaku Kenkyukai "New Processing and Modifying Technique and
Development of Uses of Water-Soluble Polymers and Aqueous Dispersion Type
Resins", Keiei Kaihatsu Center Shuppan-bu (1981); Matao Nakamura
"Water-Soluble Polymers (Suiyosei Kobunshi)" Kagaku Kogyo-sha (1973); R.
L. Davidson "Handbook of Water-Soluble Gums and Resins" McGraw-Hill Book
Company (1980); and "Encyclopedia of Polymer Science and Engineering" Vol.
3, pp. 69-270, John Wiley and Sons (1985).
Examples of the network hydrophilic resin include the foregoing natural
hydrophilic resins and derivatives thereof.
The network hydrophilic resin grains of the present invention consist of
the hydrophilic polymeric components as described above, in which polymer
molecule chains are crosslinked to form higher order network structures.
Thus, the hydrophilic resin grains are made hardly soluble or insoluble in
water, so that the solubility of the resin in water is at most 80% by
weight, preferably 50% by weight.
The crosslinking according to the present invention can be carried out by
known methods, that is, (1) method comprising crosslinking a polymer
containing the hydrophilic component with various crosslinking agents or
hardening agents, (2) method comprising polymerizing a monomer
corresponding to the hydrophilic polymeric component in the presence of a
multifunctional monomer or multifunctional oligomer containing two or more
polymerizable functional groups to form a network structure among the
molecules and (3) method comprising subjecting polymers containing the
hydrophilic polymeric components and reactive groups to polymerization
reaction or polymer reaction and thereby effecting crosslinking.
As the crosslinking agent in the above described method (1), there can be
used compounds commonly used as crosslinking agents, for example,
described in Shinzo Yamashita and Tosuke Kaneko "Handbook of Crosslinking
Agents (Kakyozai Handbook)" published by Taiseisha (1981) and Kobunshi
Gakkai Edition "High Molecular Data Handbook -Basis- (Kobunshi Data
Handbook -Kisohen-)" published by Baihunkan (1986).
Examples of the crosslinking agent are organosilane compounds such as
vinyltrimethoxysilane, vinyltributoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane, .gamma.-aminopropyltriethoxysilane
and other silane coupling agents; polyisocyanate compounds such as
tolylene diisocyanate, o-tolylene diisocyanate, diphenylmethane
diisocyanate, triphenylmethane diisocyanate, polymethylenepolyphenyl
isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high
molecular polyisocyanates; polyol compounds such as 1,4-butanediol,
polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane
and the like; polyamine compounds such as ethylenediamine,
.gamma.-hydroxypropylated ethylenediamine, phenylenediamine,
hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic
polyamines and the like; polyepoxy group-containing compounds and epoxy
resins, for example, as described in Kakiuchi Hiroshi "New Epoxy Resins
(Shin Epoxy Jushi)" published by Shokodo (1985), and Kuniyuki Hashimoto
"Epoxy Resins (Epoxy Jushi)" published by Nikkan Kogyo Shinbunsha (1969);
melamine resins such as described in Ichiro Miwa and Hideo Matsunaga "Urea
and Melamine Resins (Urea-Melamine Jushi)" published by Nikkan Kogyo
Shinbunsha (1969); and poly(meth)acrylate compounds as described in Shin
Ogawara, Takeo Saegusa and Toshinobu Higashimura "Oligomers" published by
Kodansha (1976) and Eizo Omori "Functional Acrylic Resins" published by
Technosystem (1985), for example, polyethylene glycol diacrylate,
neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane
triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether
diacrylate, oligoester acrylate and methacrylates thereof and the like.
Of the hardening agents used in the above described method (1), natural
hydrophilic resins such as gelatin, as the hardening agent, include those
described in U.S. Pat. Nos. 3,057,723; 3,671,256; 3,396,029; 4,161,407 and
4,207,109; British Patent No. 1,322,971; Japanese Patent Publication No.
17112/1967; Japanese Patent Laid-Open Publication Nos. 94817/1976,
66841/1981, 207243/1982 and 12132/1984; "The Theory of the Photographic
Process" 4th Edition (T. H. James et al.) page 94 and "Polymeric Amines
and Ammonium Salts" (E. J. Gehtals et al.) page 21.
Examples of the polymerizable function group of the multifunctional monomer
or multifunctional oligomer containing at least two polymerizable
functional groups, used in the above described method (2), are:
##STR25##
Any of monomers or oligomers containing two or more same or different ones
of these polymerizable functional groups can be used in the present
invention.
Of these monomers or oligomers, as the monomer or oligomer having two or
more same polymerizable functional groups, there can be used styrene
derivatives such as divinyl benzene and trivinyl benzene; esters of
polyhydric alcohols such as ethylene glycol, diethylene glycol,
triethylene glycol, polyethylene glycols Nos. 200, 400 and 600,
1,3-butylene glycol, neopentyl glycol, dipropylene glyclol, polypropylene
glycol, trimethylolpropane, trimethylolethane, pentaerythritol and the
like or polyhydroxyphenols such as hydroquinone, resorcinol, catechol and
derivatives thereof with methacrylic acid, acrylic acid or crotonic acid,
vinyl ethers and allyl ethers; vinyl esters of dibasic acids such as
malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
maleic acid, phthalic acid, itaconic acid and the like, allyl esters,
vinylamides and allylamides; and condensates of polyamines such as
ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and the like
with carboxylic acids containing vinyl groups such as methacrylic acid,
acrylic acid, crotonic acid, allylacetic acid and the like.
As the monomer or oligomer having two or more different polymerizable
functional groups, there can be used, for example, ester derivatives or
amide derivatives containing vinyl groups of carboxylic acids containing
vinyl group, such as methacrylic acid, acrylic acid, methacryloylacetic
acid, acryloylacetic acid, methacryloylpropionic acid, acryloylpropionic
acid, itaconyloylacetic acid and itaconyloylpropionic acid, reaction
products of carboxylic anhydrides with alcohols or amines such as
allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid,
2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid and the
like, for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate,
allyl methacrylate, allyl acrylate, allyl itaconate, vinyl
methacryloylacetate, vinyl methacryloylpropionate, allyl
methacryloylpropionate, vinyloxycarbonylmethyl methacrylate,
2-(vinyloxycarbonyl)ethyl ester of acrylic acid, N-allylacrylamide,
N-allylmethacrylamide, N-allylitaconamide, methcaryloylpropionic acid
allylamide and the like; and condensates of amino alcohols such as
aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol,
2-aminobutanol and the like with carboxylic acids containing vinyl groups.
The monomer or oligomer containing two or more polymerizable functional
groups of the present invention is generally used in a proportion of at
most 10 mole %, preferably at most 5 mole % to all monomers, which is
polymerized to form a resin.
In the present invention, there can be used a polymer containing
polymerizable double bond groups illustrative of which are the above
described similar groups. The polymerization reaction among the polymers
can be carried out jointly using the above described polymerizable
multifunctional monomer, as well known in the art.
The crosslinking of polymers by reacting reactive groups among the polymers
and forming chemical bonds according to the foregoing method (3) can be
carried out in the similar manner to the ordinary reactions of organic low
molecular compounds, for example, as disclosed in Yoshio Iwakura and
Keisuke Kurita "Reactive Polymers (Hannosei Kobunshi)" published by
Kohdansha (1977) and Ryohei Oda "High Molecular Fine Chemical (Kobunshi
Fine Chemical)" published by Kohdansha (1976). Combination of functional
groups classified as Group A (hydrophilic polymeric component) and
functional groups classified as Group B (polymers comprising components
containing reactive groups) in the following Table 1 has well been known
for effectively accomplishing the polymer reactions. In Table 1, R.sub.25
and R.sub.26 are hydrocarbon groups having the same meanings as l.sub.8
and l.sub.9 in L.sub.3 of the foregoing General Formula (V).
TABLE 1
______________________________________
Group A Group B
______________________________________
COOH, PO.sub.3 H.sub.2
##STR26##
OH, SH
NH.sub.2 COCl, SO.sub.2 Cl,
cyclic acid anhydride
SO.sub.2 H
NCO, NCS,
##STR27##
______________________________________
As illustrated above, the network hydrophilic resin grains of the present
invention are polymer grains comprising hydrophilic group-containing
polymeric components and having high order crosslinking structures among
molecular chains, and for example, hydrogels or highly hydroscopic resins
can be used therefor, as described in L. H. Sperling "Interpenetrating
Polymer Networks and Related materials" Plenum Press (1981), "Encyclopedia
of Polymer Science and Engineering" Vol. 8, pp. 279-340 (1985), J. D.
Anclrade "Hydrogels for Medical and Related Application", ACS Symposium
Series No. 31, American Chemical Society, Washington D.C. (1976), Eizo
Omori "Development Tendency and Use Development of Highly Hygroscopic
Resins (Kokyusuisei Jushi no Kaihatsu Doko to sono Yoto Tenkai)"
Technoforum Shuppanbu KK (1987), Masahiro Irie "Production and Application
of Functional High Molecular Gels (Kinosei Kobunshi Gel no Seizo to Oyo)"
published by C.M.C KK (1987), Kenji Tanaka "Petrotech." 10, 25 (1987),
"Nikkei New Materials" June 1, 1987, page 57, Jun Taguchi and Kunio Ishii
"Science and Industry (Kagaku to Kogyo)" 59, 188 (1985), Fusayoshi Masuda
"Functional Materials (Kino Zairyo)" No. 4, p. 36 (1982) and Yoshinori
Monma "Chemical Industry (Kagaku Kogyo)" 38, 602 (1987).
Examples of commercially available highly hygroscopic resins are Arasoap
(-commercial name-, made by Arakawa Kagaku Kogyo KK), Wondergel
(-commercial name-, made by Kao KK), KI Gel (-commercial name-, made by
Kurare Isoprene KK), Sanwet (-commercial name-, made by Sanyo Kasei Kogyo
KK), Sumika Gel (-commercial name, Sumitomo Kagaku Kogyo KK), Aquakeep
(-commercial name-, made by Seitetsu Kagaku Kogyo KK), Lanseal
(-commercial name-, made by Nippon Exslan Kogyo KK), Lion Polymer
(-commercial name-, made by Lion KK), GP (-commercial name, made by Nippon
Gosei Kagaku Kogyo KK), Aqualic (-commercial name-, made by Nippon
Shokubai Kagaku Kogyo KK), Aquaprene (-commercial name-, made by Meisei
Kagaku Kogyo KK), CLD (-commercial name-, made by Buckeye Cellulose Co.),
D. W. A. L. (-commercial name-, Dow Chemical Co.), G. P. C. (-commercial
name-, made by Grain Processing Co.), Aqualon (-commercial name-, made by
Hercules Co.), Magic Water Gel (-commercial name-, made by Super Adsorbent
Co.), Cecagum (-commercial name-, made by CEC Co.), Spon Signus
(-commercial name-, made by Kanegafuchi Gosei Kagaku KK), super Rub
(-commercial name-, made by Asahi Kasei Kogyo KK), etc.
In the present invention, granulation of the network hydrophilic resin
grains is carried out in the similar manner to that of the foregoing
hydrophilic resin grains.
Binder resins to be jointly used with the above described hydrophilic resin
grains or network hydrophilic resin grains will now be illustrated:
The binder resin used in the present invention is composed of at least one
of the low molecular weight Resin A having a weight average molecular
weight of 1.times.10.sup.3 to 2.times.10.sup.4, containing at least 30% by
weight of the specified polymeric components of recurring units
represented by the foregoing General Formulae (I), (Ia) and/or (Ib) and
having at least one of polar groups and/or cyclic acid anhydrides (in this
specification, "polar groups" means to include "cyclic acid anhydride"
unless otherwise indicated) bonded to one end of the polymer main chain,
and at least one of Resin B having a weight average molecular weight of at
least 3.times.10.sup.4 and consisting of a comb type copolymer containing
at least one of monofunctional macromonomers each having a weight average
molecular weight of at most 2.times.10.sup.4, having at least one of the
specified polymeric components of recurring units represented by the
foregoing General Formulae (IIa) and (IIb) and having a double bond group
bonded to only one end of the main chain, represented by the foregoing
General Formula (IIc), and at least one of the monomers represented by the
foregoing General Formula (III).
As the low molecular weight Resin A, there is preferably used a Resin A
having the polar group bonded to the end and containing the methacrylate
component having the specified substituent containing a benzene ring
having the specified substituted on 2- and/or 6-position or
non-substituted naphthalene ring, which low molecular weight polymer will
hereinafter be referred to as Resin A'.
As the high molecular weight Resin B, there is preferably used a Resin B
consisting of a comb type copolymer containing at least one of the
monofunctional Macromonomer M and at least one of the monomers represented
by General Formula (III) and having the foregoing polar group bonded to
the end of the polymer main chain, which high molecular weight polymer
will hereinafter be referred to as Resin B'.
The acid group-containing binder resin of the prior art, as described
above, has mainly been used for the offset master and has such a large
molecular weight, e.g. at least 5.times.10.sup.4 as to improve the
printing durability due to maintenance of the film strength, and these
copolymers are random copolymers in which the acid group-containing
copolymeric components are existing at random in the polymer main chain.
According to the present invention, on the other hand, it is found that
since Resin A contains methacrylate copolymeric components each having the
specified substituent and has the polar group bonded to the end of the
main chain, the polar group adsorbs on the stoichiometric defects of
photoconductive zinc oxide and the molecular weight thereof is relatively
small, so that the covering property of the surface of photoconductive
zinc oxide is improved to compensate the trap of photoconductive zinc
oxide and to markedly improve the humidity property, while dispersion of
photoconductive zinc oxide is sufficiently carried out to prevent
aggregation thereof.
Furthermore, it is found that Resin B renders sufficient the mechanical
strength of a photoconductive layer whose mechanical strength is
insufficient by only Resin A without deteriorating the excellent
electrophotographic properties by the use of Resin A. That is, in the case
of using the binder resin of the present invention, interaction of the
adsorption and coating by the inorganic photoconductive material and
binder resin can suitably be effected and the film strength of the coated
electroconductive layer can be maintained.
This is probably due to the action of the binder resin according to the
present invention as described below: That is, the intensity of the
interaction between the inorganic photoconductive material and resin can
be varied by using Resin A and Resin B as the binder resin of the
inorganic photoconductive material and specifying the weight average
molecular weight of the each resin, the content and bonded position of the
polar groups in the resin. Thus, Resin A having a stronger interaction can
selectively and suitably be adsorbed on the inorganic photoconductive
material, while Resin B having a weaker interaction than Resin A
moderately interacts with the inorganic photoconductive material to such
an extent that the polar group bonded to the specific position of the
polymer main chain in the resin does not deteriorate the
electrophotographic properties and Resin B having a long molecular chain
length and grafted chain length causes interaction of these molecular
chains with each other, whereby the electrophotographic properties and the
mechanical strength of the film can markedly be improved.
When Resin A' is particularly used as Resin A, the static properties, in
particular, D. R. and E.sub.1/10 can further be improved without
deteriorating the excellent properties obtained by the use of Resin A.
These benefits are hardly fluctuated even if the ambient conditions are
changed, for example, from high temperature and high humidity to low
temperature and low humidity.
When Resin B' is particularly used as Resin B, the static properties, in
particular, D.R. and E.sub.1/10 can further be improved as in the above
described Resin A' without deteriorating the excellent properties obtained
by the use of Resin A. These effects are hardly fluctuated even if the
ambient conditions are changed, for example, from high temperature and
high humidity to low temperature and low humidity and moreover, the film
strength as well as the printing durability can be improved.
In the present invention, the surface of the photoconductive layer is
rendered smooth. When using a photoreceptor comprising a photoconductive
layer with a low surface smoothness as an electrophotographic lithographic
printing plate precursor, the dispersion state of the photoconductive
material, i.e. inorganic grains and binder resin is not suitable and the
photoconductive layer is formed under such a state that aggregation
exists. Consequently, even if an oil-desensitizing treatment is carried
out with an oil-desensitizing solution, rendering a non-image area
hydrophilic is not uniform, nor sufficient and adhesion of a printing ink
during printing takes place to result in background stains.
The binder resin of the present invention will now be illustrated in
greater detail:
Resin A contains at least 30% by weight of the recurring units represented
by General Formula (I) as polymeric components and the specified polar
group bonded to one end of the polymer main chain, and has a weight
average molecular weight of 1.times.10.sup.3 to 2.times.10.sup.4,
preferably 3.times.10.sup.3 to 1.times.10.sup.4. In addition, Resin A has
a glass transition point of preferably -20.degree. C. to 110.degree. C.,
more preferably -10.degree. C. to 90.degree. C.
If the molecular weight of Resin A is less than 10.sup.3, the film-forming
property is too lowered to maintain a sufficient film strength, while if
more than 2.times.10.sup.4, in a photoreceptor using a near infrared to
infrared spectral sensitizing dye, fluctuation of the dark decay retention
ratio and photosensitivity under severe conditions such as high
temperature and high humidity or low temperature and low humidity is
somewhat increased and consequently, the benefit of the present invention
cannot sufficiently be obtained that a stable reproduced image can be
obtained.
In Resin A, the polymeric components corresponding to the recurring unit of
General Formula (I) are generally in a proportion of at least 30% by
weight, preferably 50 to 97% by weight and the copolymeric components
containing the polar groups are generally in a proportion of 0.5 to 15% by
weight, preferably 1 to 10% by weight.
In Resin A', the methacrylate components corresponding to the recurring
units of General Formula (Ia) and/or (Ib) are generally in a proportion of
at least 30% by weight, preferably 50 to 90% by weight and the polar
groups contained at the end of the polymer main chain are generally in a
proportion of 0.5 to 15% by weight, preferably 1 to 10% by weight based on
100% by weight of Resin A'.
If the polar group in Resin A or Resin A' is less than 0.5% by weight, the
initial potential is too low to obtain a sufficient image density, while
if more than 15% by weight, the dispersibility is lowered in spite of its
lower molecular weight, the high humidity property as to the film
smoothness and electrophotographic character is deteriorated and
background staining is increased when used as an offset master.
The recurring unit represented by the following General Formula (I),
contained in a proportion of at least 30% by weight in Resin A will now be
illustrated:
##STR28##
in which a.sub.1 and a.sub.2 each represent, same or different, hydrogen
atom, halogen atoms such as chlorine, cyano group and hydrocarbon groups,
e.g. alkyl groups containing 1 to 4 carbon atoms such as methyl, ethyl,
propyl and butyl groups, and R.sub.1 represents hydrocarbon groups, for
example, optionally substituted alkyl groups containing 1 to 18 carbon
atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl,
dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl,
2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, and 3-hydroxypropyl groups,
optionally substituted alkenyl groups containing 2 to 18 carbon atoms such
as vinyl, allyl, isopropenyl, butenyl, hexenyl, heptenyl and octenyl
groups, optionally substituted aralkyl groups containing 7 to 12 carbon
atoms such as benzyl, phenethyl, naphthylmethyl, 2-naphthylethyl,
methoxybenzyl, ethoxybenzyl and methylbenzyl groups, optionally
substituted cycloalkyl groups containing 5 to 8 carbon atoms such as
cyclopentyl, cyclohexyl and cycloheptyl groups and optionally substituted
aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl,
methoxyphenyl, ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl,
chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl,
ethoxycarbonylphenyl, cyanophenyl and nitrophenyl groups.
More preferably, in General Formula (I), one of a.sub.1 and a.sub.2 is
hydrogen atom and the other thereof is methyl group. More preferable
examples of R.sub.1 are alkyl groups containing 1 to 6 carbon atoms,
aralkyl groups containing 1 to 6 carbon atoms and aryl groups which can be
substituted.
Furthermore, preferable copolymeric components of Resin A are copolymeric
components of methacrylates containing substituted benzene rings or
naphthalene ring, represented by the following General Formula (Ia) and/or
(Ib). Resin A' contains this copolymeric component and the copolymeric
component containing the polar group.
##STR29##
In Formula (Ia), preferably, T.sub.1 and T.sub.2 each represents, same or
different, hydrogen atom, chlorine atom, bromine atom, hydrocarbon groups
containing 1 to 10 carbon atoms, more preferably alkyl groups containing 1
to 4 carbon atoms such as methyl, ethyl, propyl and butyl groups, aralkyl
groups containing 7 to 9 carbon atoms such as benzyl, phenethyl,
3-phenylpropyl, chlorobenzyl, dichlorobenzyl, bromobenzyl, methylbenzyl,
methoxybenzyl and chloromethylbenzyl groups and aryl groups such as
phenyl, tolyl, xylyl, bromophenyl, methoxyphenyl, chlorophenyl and
dichlorophenyl groups, and --COR.sub.4 and --COOR.sub.4 wherein R.sub.4 is
preferably that described for the foregoing preferable hydrocarbon groups
containing 1 to 10 carbon atoms. T.sub.1 and T.sub.2 are not
simultaneously hydrogen atoms.
In General Formulae (Ia) and (Ib), L.sub.1 and L.sub.2 each represent a
direct bond for bonding --COO-- and benzene ring or bonding groups
containing 1 to 4 bonding atoms such as (CH.sub.2 --.sub.n wherein n is an
integer of 1 to 3, --CH.sub.2 OCO--, --CH.sub.2 CH.sub.2 OCO--, (CH.sub.2
--.sub.m wherein m is an integer of 1 or 2 and --CH.sub.2 CH.sub.2 O--,
preferably a direct bond or bonding groups containing 1 or 2 bonding
atoms.
Examples of the recurring unit represented by Formula (Ia) or (Ib), used in
Resin A' of the present invention, will be given below without limiting
the same. In the following (b-1) to (b-20), n is an integer of 1 to 4, m
is 0 or an integer of 1 to 4, p is an integer of 1 to 3, R.sub.27 to
R.sub.30 each represent --C.sub.n H.sub.2n+1 or (CH.sub.2 --.sub.m C.sub.6
H.sub.5 wherein n and m have the same meaning as described above, and X
and X' each represent any of --Cl, --Br and --I.
##STR30##
The polar group bonded to one end of the polymer main chain of Resin A will
now be illustrated. The polar group is at least one member selected from
the group consisting of --PO.sub.3 H.sub.2, --SO.sub.3 H, --COOH, --OH,
##STR31##
and cyclic acid anhydride-containing groups. Preferable groups are
--PO.sub.3 H.sub.2, --SO.sub.3 H, --COOH,
##STR32##
and cyclic acid anhydride-containing groups.
In
##STR33##
group, R.sub.0 represents a hydrocarbon group or --OR.sub.0 ' wherein
R.sub.0 ' represent a hydrocarbon group. Specifically, R.sub.0 represents
optionally substituted hydrocarbon groups containing 1 to 6 carbon atoms
such as methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl,
2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, 2-methoxybutyl, benzyl,
phenyl, propenyl, methoxymethyl, ethoxymethyl and 2-methoxyethyl groups
and R.sub.0 ' has the same meaning as R.sub.0. R.sub.0 and R.sub.0 ' have
the same meaning as R.sub.9 in
##STR34##
that the foregoing hydrophilic resin grains have.
The cyclic acid anhydride-containing group means a group containing at
least one cyclic acid anhydride, illustrative of which are aliphatic
dicarboxylic acid anhydrides and aromatic dicarboxylic acid anhydrides.
Examples of the aliphatic dicarboxylic acid anhydride include rings of
succinic anhydride, glutaconic anhydride, maleic anhydride,
cyclopentane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic
anhydride, cyclohexene-1,2-dicarboxylic anhydride and
2,3-bicyclo[2,2,2]octadicarboxylic anhydride. These rings can be
substituted, for example, by halogen atoms such as chlorine and bromine
atoms and/or alkyl groups such as methyl, ethyl, butyl and hexyl groups.
Examples of the aromatic dicarboxylic acid anhydride include rings of
phthalic anhydride, naphthalene dicarboxylic anhydride, pyridine
dicarboxylic anhydride and thiophene dicarboxylic anhydride. These rings
can be substituted by, for example, halogen atoms such as chlorine and
bromine atoms, alkyl groups such as methyl, ethyl, propyl and butyl
groups, hydroxyl group, cyano group, nitro group, alkoxycarbonyl groups
wherein alkoxy groups are methoxy and ethoxy groups, and the like.
The above described polar group is bonded directly or through a suitable
bonding group to only the end of a polymer main chain containing at least
one of the polymeric components represented by, at least, General Formulae
(I), (Ia) and/or (Ib). These bonding groups include any combination of
atomic groups, for example, carbon-carbon bond (single or double bond),
carbon-hetero atom bond wherein hetero atom is, for example, oxygen
sulfur, nitrogen or silicon atom, hetero atom-hetero atom bond.
A preferable structure of the end of the polymer main chain of Resin A or
Resin A' according to the present invention is thus shown by the following
General Formula (VI):
##STR35##
In Formula (VI), a.sub.11 and a.sub.12 have the same meaning as a.sub.1
and a.sub.2 in Formula (I), Y.sub.3 has the same meaning as R.sub.1 in
Formula (I),
##STR36##
in Formula (Ia) or
##STR37##
in Formula (Ib), A represents the above described specific polar group and
L.sub.4 has the same meaning as L.sub.3 in General Formula (V) of the
hydrophilic group-containing component in the hydrophilic resin.
The moiety represented by [A-L.sub.4 ] in the above-described Formula (VI)
will further be exemplified below without limiting the scope of the
present invention. In the following examples, k.sub.1 is an integer of 1
or 2, k.sub.2 is an integer of 2 to 16 and k.sub.3 is an integer of 1 or
3.
##STR38##
Resin A or Resin A' of the present invention can contain, in addition to
the monomers of General Formulae (I), (Ia) and/or (Ib) and the monomers
containing the polar groups, other monomers as copolymeric components.
As the other copolymeric components, for example, there are given
methacrylic acid esters containing other substituents than those
represented by General Formula (I), acrylic acid esters, crotonic acid
esters, .alpha.-olefins, vinyl or allyl esters of carboxylic acids such as
acetic acid, propionic acid, butyric acid, valeic acid, benzoic acid,
naphthalene carboxylic acid and the like, acrylonitrile,
methacrylonitrile, vinyl esters, itaconic acid esters such as dimethyl
ester, diethyl ester and the like, acrylamide, methacrylamide, styrenes
such as styrene, vinyltoluene, chlorostyrene, vinyltoluene, chlorostyrene,
hydroxystyrene, N,N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
methanesulfonyloxystyrene, vinylnaphthalene and the like,
vinylsulfone-containing compounds, vinyl ketone-containing compounds,
heterocyclic vinyl compounds such as vinylpyrrolidone, vinylpyridine,
vinylimidazole, vinylthiophene, vinylimidazoline, vinylpyrazole,
vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine and the like.
Synthesis of Resin A, i.e. copolymer consisting of the above-described
copolymeric components and having the above described polar group at the
end of the main chain can readily be carried out by a method comprising
reacting the end of a living polymer obtained by the prior art anionic
polymerization or cationic polymerization with various reagents (method by
ionic polymerization), method comprising radical polymerization using a
chain transfer agent and/or polymerization initiator containing a specific
acid group in the molecule, method comprising subjecting a polymer
containing a reactive group such as amino group, halogen atoms, epoxy
group, acid halides group or the like at the end thereof, obtained by the
ionic polymerization or radical polymerization as described above, to
polymer reaction convert it into the specified polar group according to
the present invention, for example, as described in introductions and
literatures cited therein of P. Dreyfuss and R. P. Quirk, "Encycl. Polym.
Sci. Eng." 7, 551 (1987); Yoshiki Nakajo and Yuya Yamashita, "Senryo to
Yakuhin (Dyes and Chemicals)" 30, 232 (1985), Akira Ueda and Susumu Nagai
"Kagaku to Kogyo (Science and Industry)" 60, 57 (1986), etc.
As the chain transfer agent, for example, there can be used mercapto
compounds having the above-described polar group or reactive group capable
of being converted into the polar group, such as thioglycolic acid,
thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid,
3-mercaptopropionic acid, 3-mercaptobutyric acid,
N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid,
3-[N-(2-mercaptoethyl)carbamoyl]propionic acid;
3-[N-(2-mercaptoethyl)amino]propionic acid,
N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid,
3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid,
2-mercaptoethanol, 3-mercapto-1,2-propane diol, 1-mercapto-2-propanol,
3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine,
2-mercaptoimidazole, 2-mercapto-3-pyridinol,
4-(2-mercaptoethyloxycarbonyl)phthalic anhydride, 2-mercaptoethylphosphono
acid, 2-mercaptoethylphosphono acid monomethyl ester and the like, and
iodoalkyl compounds having the above described polar group or substituent,
such as iodoacetic acid, iodopropionic acid, 2-iodoethanol,
2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and the like. Above
all, the mercapto compounds are preferably used.
As the polymerization initiator containing the polar group or the specified
reactive group capable of being converted into the polar group, for
example, 4,4'-azobis(4-cyanovaleic acid), 4,4'-azobis(4-cyanovaleic acid
chloride), 2,2'-azobis(2-cyanopropanol), 2,2'-azobis(2-cyanopentanol),
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide],
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide
}, 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazoline-2-il]propane},
2,2'-azobis[2-(2-imidazoline-2-il)propane] and
2,2'-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepine-2-il)propane].
These chain transfer agents or polymerization initiators are generally used
in a proportion of 0.5 to 15 parts by weight, preferably 2 to 10 parts by
weight to 100 parts by weight of all the monomers.
Resin B will be illustrated. Resin B consists of a comb type copolymer
having a weight average molecular weight of 3.times.10.sup.4 to
1.times.10.sup.6, preferably 5.times.10.sup.4 to 5.times.10.sup.5 and
being obtained by copolymerizing a monofunctional macromonomer containing
at least one of polymeric components represented by General Formulae (IIa)
and (IIb) and a polymerizable double bond group represented by General
Formula (IIc) at the terminal of the polymer main chain with a monomer
represented by General Formula (III). The glass transition point of Resin
B is in the range of preferably 0.degree. to 110.degree., more preferably
20.degree. to 90.degree..
If the molecular weight of Resin B is less than 3.times.10.sup.4, the film
strength cannot be maintained sufficient, while if more than
1.times.10.sup.6, the dispersibility is deteriorated, the film smoothness
is lowered, the image quality of a reproduced image, in particular,
reproducibility of fine lines and letters is deteriorated and background
staining is remarkable when used as an offset master
The polar group content in Resin B' is preferably at most 5% by weight,
more preferably at most 2% by weight to 100% by weight of resin B', since
if more than 5% by weight, there occurs aggregation or precipitation of
the dispersion for forming the light-sensitive layer, or the
dispersibility is lowered to thus deteriorate the film smoothness and
electrophotographic properties.
Firstly, the copolymeric component of the comb type copolymer, Resin B,
i.e. macromonomer M will be illustrated in detail. The monofunctional
macromonomer M is a compound having a polymerizable double bond group
represented by General Formula (IIc), bonded to only one end of a polymer
main chain containing at least one of polymeric components represented by
General Formula (IIa) or (IIb), and having a weight average molecular
weight of at most 2.times.10.sup.4 :
##STR39##
In General formulae (IIa), (IIb) and (IIc), the hydrocarbon groups
contained in a.sub.3, a.sub.4, a.sub.5, a.sub.6, b.sub.1, b.sub.2,
X.sub.0, Q.sub.0 and Q.sub.1 respectively have the number of carbon atoms,
as described above, in the form of the non-substituted hydrocarbon groups
and optionally can be substituted.
In General Formula (IIc) representative of the polymerizable property of
the macromonomer M, V represents --COO--, --OCO--, --(CH.sub.2).sub.1
--OCO--, --(CH.sub.2).sub.1 --COO--, --O--, --CONHCOO--, --CONHCONH--,
--SO.sub.2 --, --CO--,
##STR40##
wherein R.sub.2 represents hydrogen atom or hydrocarbon group or
##STR41##
In these formulae, l represents an integer of 1 to 3 and R.sub.2 has the
same meaning as R.sub.19 in General Formula (V) when R.sub.2 is a
hydrocarbon group.
When V is
##STR42##
the benzene ring can have a substituent illustrative of which are halogen
atoms such as chlorine and bromine atoms, alkyl groups such as methyl,
ethyl, propyl, butyl, chloromethyl, methoxymethyl groups and the like, and
alkoxy groups such as methoxy, ethoxy, propioxy, butoxy and the like.
b.sub.1 and b.sub.2 each represent preferably, same or different, hydrogen
atom, halogen atoms such as chlorine and bromine atoms, cyano group, alkyl
groups containing 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl
and the like, --COOR.sub.3 and --COOR.sub.3 through a hydrocarbon group,
wherein R.sub.3 represents hydrogen atom, alkyl group containing 1 to 18
carbon atoms, alkenyl group, aralkyl group, alicyclic group or aryl group,
which can be substituted, and specifically, has the same meaning as
R.sub.19 in General Formula (V).
Examples of the hydrocarbon group in the --COO--R.sub.3 group through a
hydrocarbon group are methylene, ethylene, propylene groups and the like.
In General Formula (IIc), more preferably, V represents --COO--, --OCO--,
--CH.sub.2 OCO--, --CH.sub.2 COO--, --O--, --CONH--, --CONHCOO--,
--SO.sub.2 NH-- or
##STR43##
b.sub.1 and b.sub.2 each represent, same or different, hydrogen atom,
methyl group, --COOR.sub.3 ' or --CH.sub.2 COOR.sub.3 ' wherein R.sub.3 '
represents hydrogen atom or an alkyl group containing 1 to 6 carbon atoms
such as methyl ethyl, propyl, butyl, hexyl group or the like. More
preferably, one of b.sub.1 and b.sub.2 is surely hydrogen atom.
In General Formula (IIa) representing the copolymeric component to be the
recurring unit contained in the macromonomer M, X.sub.0 has the same
meaning as V in the foregoing Formula (IIc), a.sub.3 and a.sub.4 each have
the same meaning as a.sub.1 and a.sub.2 in Formula (I), which can be same
or different, and Q.sub.0 represents an aliphatic group containing 1 to 18
carbon atoms or an aromatic group containing 6 to 12 carbon atoms and
specifically represents the same meaning as R.sub.1 in Formula (I).
When Q.sub.0 is an aliphatic group, more preferably, it represents an alkyl
group containing 1 to 5 carbon atoms, alkenyl group containing 3 to 6
carbon atoms and aralkyl group containing 7 to 9 carbon atoms, and when
Q.sub.0 is an aromatic group, it includes all the examples described
above.
In Formula (IIa), preferably X.sub.0 represents --COO--, --OCO--,
--CH.sub.2 OCO--, --CH.sub.2 COO--, --O--, --CO--, --CONH--, --SO.sub.2
NH-- or
##STR44##
In General Formula (IIb) representing the copolymeric component to be the
recurring unit contained in the macromonomer M, Q.sub.1 represents --CN,
--CONH.sub.2 or
##STR45##
and examples of Y are halogen atoms such as chlorine and bromine atoms,
alkyl groups such as methyl, ethyl, propyl, butyl, chloromethyl,
methoxymethyl groups and the like and alkoxy groups such as methoxy,
ethoxy, propioxy, butoxy groups and the like, which are the same as the
examples of the substituents when V in Formula (IIc) is
##STR46##
The macromonomer M can contain two or more polymeric components represented
by Formula (IIa) or (IIb). In Formula (IIa), when Q.sub.0 is an aliphatic
group, the aliphatic group containing 6 to 12 carbon atoms is preferably
in a proportion of less than 20% by weight of all the polymeric components
in the macromonomer M.
Furthermore, when X.sub.0 represent --COO-- in General Formula (IIa), the
polymeric component represented by General Formula (IIa) is preferably
contained in a proportion of at least 30% by weight in all the polymeric
components in the macromonomer M.
In the macromonomer M, as the monomer corresponding to the recurring unit
copolymerizable with the polymeric component represented by General
Formula (IIa) and/or (IIb), there can be used those similar to exemplified
as the other monomer which can be contained as the copolymeric component
with the monomer represented by General Formula (Ia) and/or (Ib) and the
monomer containing the polar group of Resin A.
In the present invention, the macromonomer M has such a chemical structure
that the polymerizable double bond group represented by General Formula
(IIc) is bonded directly or through a suitable bonding group to only one
end of the polymer main chain consisting of the recurring units
represented by General Formulae (IIa) and/or (IIb). The bonding group of
the component of Formula (IIa) and the component of Formula (IIa) or (IIb)
includes carbon-carbon bond (single or double bond), carbon-hetero atom
(hetero atom being, for example, sulfur, oxygen, nitrogen, silicon atoms,
etc.) and hetero atom-hetero atom in suitable combination.
A preferable example of the macromonomer M of the present invention is as
represented by the following General Formula (VII):
##STR47##
in which a.sub.13 and a.sub.14 each have the same meaning as a.sub.3 and
a.sub.4 or a.sub.5 and a.sub.6 in Formula (IIa) or (IIb), i.e. a.sub.1 and
a.sub.2 in Formula (I), b.sub.3 and b.sub.4 each have the same meaning as
b.sub.1 and b.sub.2 in Formula (IIc), V has the same meaning as V in
Formula (IIc), T.sub.3 represents --X.sub.0 --Q.sub.0 in Formula (IIa) or
--Q.sub.1 in Formula (IIb) and L.sub.6 has the same meaning as L.sub.3 in
Formula (V).
Examples of the recurring unit represented by General Formula (IIa) or
(IIb), contained as the copolymeric component in the macromonomer M of the
present invention, are given below without limiting the scope of the
present invention. In the following units (d-1) to (d-21), R.sub.37
represents --C.sub.n H.sub.2n+1 (n: integer of 1 to 6), a represents --H
or --CH.sub.3 and k.sub.4 represents an integer of 2 to 10.
##STR48##
Examples of the macromonomer M of the present invention, represented by
General Formula (VII), are given below without limiting the scope of the
present invention. In the following compounds (e-1) to (e-31), b
represents --H or --CH.sub.3, n represents an integer of 1 to 12 and m
represents an integer of 2 to 12.
##STR49##
The macromonomer M of the present invention can be prepared by the known
synthesis methods, for example, an ionic polymerization method comprising
reacting the end of a living polymer obtained by anionic or cationic
polymerization with various reagents to obtain a macromer, a radical
polymerization method comprising reacting a reactive group-terminated
oligomer obtained by radical polymerization using a polymerization
initiator and/or chain transfer agent containing a reactive group such as
carboxyl, hydroxyl or amino group in the molecule with various reagents to
obtain a macromer, a polyaddition-condensation method comprising
subjecting an oligomer obtained by polyaddition or polycondensation to the
radical polymerization as described above to introduce a polymerizable
double bond group therein.
These methods are described, for example, in introductions and literatures
cited therein of P. Dreyfuss & R. P. Quirk, "Encycl. Polym. Sci. Eng.", 7,
551 (1987), P. F. Rempp E. Franta, "Adu., Polym. Sci." 58, 1 (1984), V.
Percec, "Appl. Polym. Sci." 285, 95 (1984), R. Asami and M, Takagi,
"Makromol. Chem. Suppl." 12, 163 (1985), P. Rempp. et al., "Makromol.
Chem. Suppl." 8, 3 (1984), Yusuke Kawakami, "Kagaku Kogyo (Chemical
Industry)" 38, 56 (1987), Yuya Yamashita, "Kobunshi (macromolecules)" 31,
988 (1982), Shiro Kobayashi, "Kobunshi (Macromolecules)" 30, 625 (1982),
Toshinobu Higashimaru, "Nippon Secchaku Kyokai-shi (Japan Adhesive
Association)" 18, 536 (1982), "Kobunshi Kako (Macromolecule Processing)"
35, 262 (1986), Shiro Toki and Takashi Tsuda "Kino Zairyo (Functional
Materials)" 1987, No. 10, 5, etc.
The monomer represented by General Formula (III), which is to be the
copolymeric component of the comb type polymer with the above described
macromonomer, will be illustrated in detail:
In General Formula (III), X.sub.1 has the same meaning as X.sub.o in
Formula (IIa) and preferably represents --COO--, --OCO--, --CH.sub.2
OCO--, --CH.sub.2 COO--, --O-- or
##STR50##
Q.sub.2 has the same meaning as Q.sub.o in Formula (IIa) and represents
specific and preferable examples, same as those illustrated in Q.sub.o and
a.sub.7 and a.sub.8 each represent, same or different, those defined as
a.sub.1 and a.sub.2 in Formula (I). Preferably, any one of a.sub.7 and
a.sub.8 represents hydrogen atom.
The foregoing comb type copolymer can further contain, in addition to the
monomer represented by General Formula (III), other monomers
copolymerizable with this monomer. The other monomers specifically include
those illustrated as the other monomers to be copolymerized with the
polymeric components represented by General Formulae (IIa) and/or (IIb) of
the macromonomer M. These are also similar to the other monomers which can
be contained with the copoloymeric components represented by General
Formulae (I), (Ia) and (Ib) in Resin A. In the comb type copolymer, the
other monomers are preferably in a proportion of at most 30% by weight of
all the polymeric components.
Further, the comb type copolymer of Resin B according to the present
invention can contain a specific polar group bonded to only one end of the
o polymer chain (Resin B').
Examples of the polar group are --PO.sub.3 H.sub.2, --SO.sub.3 H, --COOH,
--OH, --SH,
##STR51##
wherein R.sub.5 represents a hydrocarbon group or --OR.sub.5 ' wherein
R.sub.5 ' represents a hydrocarbon group, cyclic acid anhydride-containing
groups, --CHO, --CONH.sub.2, --SO.sub.2 NH.sub.2 and
##STR52##
wherein R.sub.6 and R.sub.7 each represents, same or different, hydrogen
atom or a hydrocarbon group. Preferable examples thereof are PO.sub.3
H.sub.2, --SO.sub.3 H, --COOH and
##STR53##
The content of
##STR54##
is the same as defined in the components containing the polar groups of
Resin A.
The polar group is chemically bonded directly or through a suitable bonding
group to one end of the polymer main chain. The group for bonding the
polymer main chain and polar group is composed of carbon-carbon bond
(single or double bond), carbon-hetero atom bond (hetero atom: oxygen,
sulfur, nitrogen silicon atoms, etc.) and hetero atom-hetero atom, in
suitable combination.
Of the comb type copolymer containing the specified polar group bonded to
one end of the polymer main chain, preferable examples are as represented
by General Formula (VIIIa) or (VIIIb):
##STR55##
In General Formulae (VIIIa) and (VIIIb), a.sub.7 ', a.sub.8 ', X.sub.1 '
and Q.sub.2 ' respectively have the same meanings as the corresponding
a.sub.7, a.sub.8, X.sub.1 and Q.sub.2 in formula (III), represented as the
polymeric component in Resin B, and a.sub.13 ', a.sub.14 ', b.sub.3 ',
b.sub.4 ', v', L.sub.6 ' and T.sub.3 ' respectively have the same meanings
as the corresponding a.sub.13, a.sub.14, b.sub.3, b.sub.4, V, L.sub.6 and
T.sub.3 in Formula (VII), represented as the preferable macromonomer. A'
represents the foregoing polar group bonded to the end of the polymer main
chain. L.sub.7 represents a mere bond or group for bonding the specific
polar group (A') and polymer main chain and specifically represents the
same content as L.sub.4 in Formula (VI) representing the terminal
structure of Resin A. Furthermore, examples of A'-L.sub.7 are the same as
those of A-L.sub.4 - described in Formula (VI).
Preferably, the comb type copolymer having the specific polar group bonded
to the end of the polymer main chain, that is, Resin B' does not contain
copolymeric components containing polar groups such as phosphono,
carboxyl, sulfo, hydroxyl, formyl, amino,
##STR56##
and the like.
Production of the comb type polymer B' having the specific polar group
bonded to only one end of the polymer chain can readily be carried out in
known manner, for example, by the similar method to illustrated in the
case of Resin A. However, the weight average molecular weight of the
polymer can be adjusted to 3.times.10.sup.4 or more by controlling the
variety and quantity of a polymerization initiator, the polymerization
initiating speed and the quantity of a chain transfer agent. For example,
the quantity of a chain transfer agent or polymerization initiator
containing the specific polar group according to the present invention is
preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by
weight per 100 parts by weight of all the monomers.
In the present invention, other resins can jointly be used in addition to
Resin A including Resin A' and Resin B including Resin B' according to the
present invention. Examples of the other resins are alkyd resins,
polybutyral resins, polyolefin resins, ethylene-vinyl acetate copolymers,
styrene resins, styrene-butadiene resins, acrylatebutadiene resins,
alkanic acid vinyl resins and the like.
When the quantity of the above described other resin exceeds 30% by weight
of the whole quantity of the binder resin comprising the resins of the
present invention, the benefits of the present invention, in particular,
improvement of the static property will be lost.
The proportion of Resin A including Resin A' and Resin B including Resin
B', depending upon the grain diameter and surface state of photoconductive
zinc oxide used, is generally in the range of 5-80 to 95-20 (by weight),
preferably 10-60 to 90-40 (by weight).
The quantity of the binder resin used for photoconductive zinc oxide is
generally in a proportion of 10 to 100 parts by weight of the binder
resin, preferably 15 to 50 parts by weight to 100 parts by weight of the
photoconductive zinc oxide.
In the present invention, if necessary, various coloring matters or dyes
can be used as a spectro sensitizer, illustrative of which are carbonium
dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes,
phthalein dyes, polymethine dyes such as oxonol dyes, merocyanine dyes,
cyanine dyes, rhodacyanine dyes, styryl dyes, etc. and phthalocyanine dyes
which can contain metals, as described in Harumi Miyamoto and Hidehiko
Takei "Imaging" No. 8, page 12 (1973), C. Y. Young et al. "RCA Review" 15,
469 (1954), Kohei Kiyota et al. "Denki Tsushin Gakkai Ronbunshi" J63-C
(No. 2), 97 (1980), Yuji Harasaki et al. "Kogyo Kagaku Zasshi" 66, 78 and
188 (1963) and Tadaaki Tani "Nippon Shashin Gakkaishi" 35, 208 (1972).
For example, those using carbonium dyes, triphenylmetahe dyes, xanthene
dyes or phthalein dyes are described in Japanese Patent Publication No.
452/1976, Japanese Patent Laid-Open Publication Nos. 90334/1975,
114227/1975, 39130/1978, 82353/1978 and 16456/1982 and U.S. Pat. Nos.
3,052,540 and 4,054,450.
As the polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes
and rhodacyanine dyes, there can be used dyes described in F. M. Harmmer
"The Cyanine Dyes and Related Compounds" and specifically dyes described
in U.S. Pat. Nos. 3,047,384, 3,110,591, 3,121,008, 3,125,447, 3,128,179,
3,132,942 and 3,622,317; British Patent Nos. 1,226,892, 1,309,274 and
1,405,898; and Japanese Patent Publication Nos. 7814/1973 and 18892/1980.
The polymethine dyes capable of spectrally sensitizing near infrared
radiations to infrared radiations with longer wavelengths of at least 700
nm are described in Japanese Patent Publication No. 41061/1976; Japanese
Patent Laid-Open Publication Nos. 840/1972, 44180/1972, 5034/1974,
45122/1974, 46245/1982, 35141/1981, 157254/1982, 26044/1986 and
27551/1986; U.S. Pat. Nos. 3,619,154 and 4,175,956; and "Research
Disclosure" 216, pages 117-118 (1982).
The photoreceptor of the present invention is excellent in that its
performance is hardly fluctuated even if it is used jointly with various
sensitizing dyes. Furthermore, various additives for electrophotographic
light-sensitive layers, such as chemical sensitizers, well known in the
art can jointly be used as occasion demands, for example, electron
accepting compounds such as benzoquinone, chloranil, acid anhydrides,
organic carboxylic acids and the like, described in the foregoing
"Imaging" No. 8, page 12 (1973) and polyarylalkane compounds, hindered
phenol compounds, p-phenylenediamine compounds and the like, described in
Hiroshi Komon et al. "Latest Development and Practical Use of
Photoconductive Materials and Light-Sensitive Materials (Saikin no
Kododenzairyo to Kankotai no Kaihatsu to Jitsuyoka)" Sections 4 to 6,
published by Nippon Kagaku Joho Shuppanbu (1986).
The amounts of these additives are not particularly limited, but are
generally 0.0001 to 2.0 parts by weight based on 100 parts by weight of
the photoconductive zinc oxide.
The thickness of the photoconductive layer is generally 1 to 100 .mu.m,
preferably 10 to 50 .mu.m.
When in a photoreceptor of laminate type consisting of a charge generating
layer and charge transporting layer, a photoconductive layer is used as
the charge producing layer, the thickness of the charge producing layer is
generally 0.01 to 1 .mu.m, preferably 0.05 to 0.5 .mu.m.
In the present invention, an insulating layer can be provided for the
purpose of mainly protecting the photoreceptor and improving the
durability and dark decay property, during which the insulating layer has
a relatively small thickness. In the case of using the photoreceptor for a
specific electrophotographic process, on the other hand, a relatively
thick insulating layer is provided, preferably with a thickness of 5 to 70
.mu.m, particularly 10 to 50 .mu.m.
As the charge transporting material of the laminate type photoreceptor,
there are preferably used polyvinylcarbazole, oxazole, dyes, pyrazoline
dyes, triphenylmethane dyes and the like. The charge transporting layer
has generally a thickness of 5 to 40 .mu.m, preferably 10 to 30 .mu.m.
Typical examples of the resin used for forming the insulating layer or
charge transporting layer are themoplastic resins and thermosetting resins
such as polystyrene resins, polyester resins, cellulose resins, polyether
resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl
acetate copolymer resins, polyacrylic resins, polyolefin resins, urethane
resins, epoxy resins, melamine resins and silicone resins.
The photoconductive layer of the present invention can be provided on a
support as well known in the art. Generally, a support for an
electrophotographic light-sensitive layer is preferably electroconductive
and as the electroconductive support, there can be used, as known in the
art, metals or substrates such as papers, plastic sheets, etc. which are
made electroconductive by impregnating low resistance materials therein,
substrates whose back surface, opposite to the surface to be provided with
a light-sensitive layer, is made electroconductive, which is further
coated with at least one layer for the purpose of preventing it from
curling; the above described support provided with, on the surface
thereof, a water proof adhesive layer; the above described support
optionally provided with, on the surface layer, one or more pre-coat
layer; and papers laminated with plastics which are made
electroconductive, for example, by vapor deposition of Al or the like
thereon. Examples of the substrates or materials which are
electroconductive or made electroconductive are described in Yukio Sakamot
"Electrophotography (Denshi Shashin)" 14 (No. 1), pages 2 to 11 (1975),
Hiroyuki Moriga "Introduction to Chemistry of Special Papers (Nyumon
Tokushushi no Kagaku)" Kobunshi Kankokai (1975), M. F. Hoover "J.
Macromol. Sci. Chem." A-4 (6), pp. 1327-1417 (1970), etc.
Production of a lithographic printing plate using the electrophotographic
lithographic printing plate precursor of the present invention can be
carried out in known manner. That is, the electrophotographic lithographic
printing plate precursor is electrostatically charged substantially
uniformly in a dark place and imagewise exposed to form an electrostatic
latent image by an exposing method, for example, by scanning exposure
using a semiconductor laser, He-Ne laser, etc., by reflection imagewise
exposure using a xenon lamp, tungsten lamp, fluorescent lamp, etc. as a
light source or by contact exposure through a transparent positive film.
The resulting electrostatic latent image is developed with a toner by any
of various known development methods, for example, cascade development,
magnetic brush development, powder cloud development, liquid development,
etc. Above all, the liquid development method capable of forming a fine
image is particularly suitable for making a printing plate. The thus
formed toner image can be fixed by a known fixing method, for example,
heating fixation, pressure fixation, solvent fixation, etc.
The printing plate having the toner image, formed in this way, is then
subjected to a processing for rendering hydrophilic the non-image area in
conventional manner using the so-called oil-desensitizing solution. The
oil-desensitizing solution of this kind include processing solutions
containing, as a predominant component, cyanide compounds such as
ferrocyanides or ferricyanides, cyanide-free processing solutions
containing, as a predominant component, ammine cobalt complexes, phytic
acid or its derivatives or guanidine derivatives, processing solutions
containing, as a predominant component, organic acids or inorganic acids
capable of forming chelates with zinc ion, and processing solutions
containing water-soluble polymers.
For example, the cyanide compound-containing processing solutions are
described in Japanese Patent Publication Nos. 9045/1969 and 39403/1971 and
Japanese Patent Laid-Open Publication Nos. 76101/1977, 107889/1982 and
117201/1979. The phytic acid or its derivatives-containing processing
solutions are described in Japanese Patent Laid-Open Publication Nos.
83807/1978, 83805/1978, 102102/1978, 109701/1978, 127003/1978, 2803/1979
and 44901/1979. The metal complex, e.g., cobalt complex-containing
processing solutions are described in Japanese Patent Laid-Open
Publication Nos. 104301/1978, 140103/1978 and 18304/1979 and Japanese
Patent Publication No. 28404/1968. The inorganic acid- or organic
acid-containing processing solutions are described in Japanese Patent
Publication Nos. 13702/1964, 10308/1965, 28408/1968 and 26124/1965 and
Japanese Patent Laid-Open Publication No. 118501/1976. The guanidine
compound-containing processing solutions are described in Japanese Patent
Laid-Open Publication No. 111695/1981. The water-soluble
polymer-containing processing solutions are described in Japanese Patent
Laid-Open Publication Nos. 36402/1974, 126302/1977, 134501/1977,
49506/1978, 59502/1978 and 104302/1978 and Japanese Patent Publication
Nos. 9665/1963, 22263/1964, 763/1965 and 2202/1965.
The oil-desensitizing treatment can generally be carried out at a
temperature of about 10.degree. C. to about 50.degree. C., preferably from
20.degree. C. to 35.degree. C., for a period of not longer than about 5
minutes.
In any of the above described oil-desensitizing solutions, the zinc oxide
in the surface layer as the photoconductive is ionized to be zinc ion
which causes a chelation reaction with a compound capable of forming a
chelate in the oil-desensitizing solution to form a zinc chelate compound.
This is precipitated in the surface layer to render the non-image area
hydrophilic.
Thus, the printing plate precursor of the present invention can be
converted into a printing plate by the oil-desensitizing processing with
an oil-desensitizing solution.
The present invention will now be illustrated in greater detail by way of
examples, but it should be understood that the present invention is not
limited thereto.
EXAMPLES
Preparation Example 1 of Hydrophilic Resin Grains
A mixed solution of 95 g of dodecyl methacrylate, 5 g of acrylic acid and
200 g of toluene was heated to 70.degree. C. while stirring under a
nitrogen stream, and 1.5 g of azobis(isobutyronitrile) (referred to as
A.I.B.N.) was added thereto and reacted for 8 hours. To this reaction
mixture were added 12 g of glycidyl methacrylate, 1 g of
t-butylhydroquinone and 0.8 g of N,N-dimethyldodecylamine, followed by
allowing the mixture to react at 100.degree. C. for 15 hours (Dispersed
Resin .alpha.).
A mixture of 7.5 g (as solid content) of the above described Dispersed
Resin .alpha., 50 g of 2-hydroxyethyl methacrylate and 200 g of n-heptane
was heated to 65.degree. C. while stirring under a nitrogen stream, and
0.7 g of 2,2-azobis(isovaleronitrile) (referred to as A. I. V. N.) was
then added thereto and reacted for 6 hours.
After passage of 20 minutes from the addition of the initiator (A. I. V.
N.), the homogeneous solution became slightly opaque, the reaction
temperature being raised to 90.degree. C. After cooling, the reaction
product was passed through a nylon cloth of 200 mesh to obtain a white
dispersion having an average grain diameter of 0.19 .mu.m as a white
latex.
Preparation Example 2 of Resin Grains
A mixture of 50 g of 2-phosphonoethyl methacrylate, 8 g of Dispersed Resin
.alpha. (as solid content), 150 g of ethyl acetate and 200 g of n-hexane
was heated to 55.degree. C. while stirring under a nitrogen stream, and
0.5 g of A. I. V. N. was added thereto and reacted for 4 hours, thus
obtaining a white dispersion. After cooling, the reaction product was
passed through a nylon cloth of 200 mesh. The resulting dispersion was a
latex with an average grain diameter of 0.45 .mu.m.
Preparation Example 3 of Resin Grains
Preparation Example 1 was repeated except using a mixture of 50 g of
N-vinylpyrrolidone, 10 g of Dispersed Resin .alpha. (as solid content) and
200 g of toluene, thus obtaining a white latex with an average grain size
of 0.30 .mu.m.
Preparation Example 4 of Resin Grains
A mixture of 31.5 g of ethylene glycol, 51.8 g of phthalic anhydride, 6.0 g
of methacrylic acid, 10 g of trichloroethylene and 0.7 g of
p-toluenesulfonic acid was heated and reacted for 6 hours in such a manner
that the reaction temperature was raised from 107.degree. C. to
150.degree. C. in 6 hours, while removing water byproduced by the reaction
by the Dean-Stark method.
A mixture of 6 g of methacrylic acid, 76 g of chloroform, 11.6 g of ethanol
and 5.8 g of Dispersed Resin .beta. obtained by the above described
reaction (as solid content) was then refluxed under a nitrogen stream. 0.8
g of A. I. B. N. was then added thereto and reacted for 3 hours to obtain
a white dispersion, latex with an average grain diameter of 0.40 .mu.m.
Preparation Example 5 of Resin Grains
Preparation Example 1 was repeated except using a mixture of 50 g of
N,N-dimethylaminoethyl methacrylate, 15 g of poly(dodecyl methacrylate)
and 300 g of toluene, thus obtaining a white dispersion with an average
grain diameter of 0.28 .mu.m.
Preparation Example 6 of Resin Grains
A mixture of 10 g of (2-hydroxyethyl acrylate/methyl methacrylate)
copolymer (weight ratio 1/1) powder, 2 g of (dodecyl methacrylate/acrylic
acid) copolymer (weight ratio 95/5) and 100 g of toluene was ball milled
for 48 hours to obtain a dispersion, i.e. latex with an average grain
diameter of 0.38 .mu.m.
Preparation Example 7 of Resin Grains
A mixture of 10 g of (vinyl alcohol/methacrylic acid) copolymer (weight
ratio 7/3), 1.8 g of (decyl methacrylate/N,N-dimethylaminoethyl acrylate)
copolymer weight ratio 95/5) and 100 g of toluene was ball milled for 56
hours to obtain a dispersion, latex with an average grain diameter of 0.32
.mu.m.
Preparation Example 8 of Resin Grains
Preparation Example 1 was repeated except adding 1 g of ethylene glycol
dimethacrylate to Dispersed Resin .alpha. in addition to the
2-hydroxyethyl methacrylate and n-heptane, thus obtaining latex grains
with an average grain diameter of 0.25 .mu.m.
Preparation Example 9 of Resin Grains
Preparation Example 2 was repeated except adding 1.2 g of divinylbenzene to
Dispersed Resin .alpha. in addition to the 2-phosphonoethyl methacrylate,
ethyl acetate and n-hexane, thus obtaining latex grains with an average
grain diameter of 0.40 .mu.m.
Preparation Example 10 of Resin Grains
Preparation Example 3 was repeated except adding 1.5 g of ethylene glycol
dimethacrylate to Dispersed Resin .alpha. in addition to the
N-vinylpyrrolidone and toluene, thus obtaining latex grains with an
average grain diameter of as that of Preparation Example 3.
Preparation Example 11 of Resin Grains
Preparation Example 4 was repeated except adding 0.05 g of 1,6-hexane diol
diacrylate to Dispersed Resin .beta. in addition to the methacrylic acid,
chloroform and ethanol, thus obtaining latex grains with an average grain
diameter of 0.45 .mu.m.
Preparation Example 12 of Resin Grains
Preparation Example 5 was repeated except adding 0.8 g of triethylene
glycol dimethacrylate, thus obtaining latex grains with an average grain
diameter of 0.43 .mu.m.
Preparation Example 13 of Resin Grains
A mixed solution of 50 g of the following monomer (a), 30 g of methyl
methacrylate, 17 g of 2-hydroxyethyl methacrylate, 3 g of allyl
methacrylate and 300 g of tetrahydrofuran was heated to 80.degree. C.
under a nitrogen stream. 1.5 g of A. I. B. N. was added thereto and
reacted for 6 hours, then subjected to reprecipitation in hexane and
filtering to obtain a solid product, which was then dried, thus obtaining
84 g of a powder.
##STR57##
Preparation Example 14 of Resin Grains
A mixture of 50 g of (2-hydroxypropyl methacrylate/ethyl methacrylate)
copolymer (weight ratio 1/3) and 200 g of methyl cellosolve was heated at
40.degree. C. and dissolved. 1.0 g of 1,6-hexamethylene diisocyanate was
added thereto and stirred for 4 hours. The resulting mixture was cooled
and then subjected to reprecipitation in water and filtration to obtain a
solid product, which was then dried, thus obtaining 35 g of a powder.
Preparation Example 15 of Resin Grains
A mixture of 5 g of 2-methyl-2-oxazoline, 1.0 g of
1,4-tetramethylene-2,2'-bisoxazoline, 0.1 g of methyl p-toluenesulfonate
and 20 g of acetonitrile was subjected to sealing polymerization. The
resulting reaction product was then subjected to reprecipitation in
methanol and a solid product was collected by filtering and dried to
obtain 4.1 g of a powder.
The resin obtained in this preparation example is a hydrogel having the
following structure:
##STR58##
Preparation Example 16 of Resin Grains
A mixed solution of 50 g of 2-methanesulfonylethyl methacrylate, 0.8 g of
divinyl succinate and 200 g of dimethylformamide was heated at 70.degree.
C. under a nitrogen stream and 1.5 g of A. I. B. N. was added thereto and
reacted for 8 hours. The resulting reaction product was subjected to a
reprecipitation treatment in hexane and a solid product was collected by
filtering and dried to obtain 38 g of a powder.
Synthetic Example 1 of Resin A: Resin A-1
A mixed solution 96 g of benzyl methacrylate, 4 g of thiosalicylic acid and
200 g of toluene was heated at a temperature of 75.degree. C. under a
nitrogen stream. 1.0 g of A. I. B. N. was added thereto and reacted for 4
hours, 0.4 g of A. I. B. N. was further added and stirred for 3 hours and
0.2 g of A. I. B. N. was then added and stirred for 3 hours. The resulting
copolymer (A-1) has the following structure and a weight average molecular
weight Mw of 6.8.times.10.sup.3 :
##STR59##
Synthetic Examples 2 to 13 of Resin A: Resins A-2 to A-13
Synthetic Example 1 was repeated except using monomers shown in the
following Table 2 instead of 96 g of benzyl methacrylate, thus obtaining
Resins A-2 to A-13. Each of these resins had Mw of 6.0.times.10.sup.3 to
8.times.10.sup.3.
TABLE 2
__________________________________________________________________________
##STR60##
Synthetic
Example
of Resin A
Resin [A]
R.sub.42 Y.sub.7 x/y
__________________________________________________________________________
2 [A-2]
C.sub.2 H.sub.5
-- 96/0
3 [A-3]
C.sub.6 H.sub.5
-- 96/0
4 [A-4]
##STR61## -- 96/0
5 [A-5]
##STR62## -- 96/0
6 [A-6]
CH.sub.3
##STR63##
86/10
7 [A-7]
C.sub.2 H.sub.5
##STR64##
86/10
8 [ A-8]
##STR65##
##STR66##
66/30
9 [A-9]
##STR67## -- 96/0
10 [A-10]
##STR68## -- 96/0
11 [A-11]
##STR69## -- 96/0
12 [A-12]
##STR70##
##STR71##
76/20
13 [A-13]
(CH.sub.2).sub.2OC.sub.6 H.sub.5
-- 96/0
__________________________________________________________________________
Synthetic Examples 14 to 24 of Resin A: Resins A-14 to A-24
Synthetic Example 1 was repeated except using methacrylates and mercapto
compounds as shown in Table 3 instead of 46 g of benzyl methacrylate and 4
g of thiosalicylic acid and using 150 g of toluene and 50 g of isopropanol
instead of 200 g of toluene, thus obtaining Resins A-14 to A-24.
TABLE 3
__________________________________________________________________________
##STR72##
Synthetic
Example
of Resin A
Resin A
W (amount)
R.sub.43 (amount)
Mw
__________________________________________________________________________
14 [A-14]
HOOCCH.sub.2 CH.sub.2 CH.sub.2
4 g C.sub.2 H.sub.5
96 g 7.3 .times. 10.sup.3
15 [A-15]
HOOCCH.sub.2 5 g C.sub.3 H.sub.7
95 g 5.8 .times. 10.sup.3
16 [A-16]
##STR73## 5 g CH.sub.2 C.sub.6 H.sub.5
95 g 7.5 .times. 10.sup.3
17 [A-17]
HOOCCH.sub.2 CH.sub.2
5.5
g C.sub.6 H.sub.5
94.5
g 6.5 .times. 10.sup.3
18 [A-18]
HOOCCH.sub.2 4 g
##STR74## 96 g 5.3 .times. 10.sup.3
19 [A-19]
##STR75## 3 g
##STR76## 97 g 6.6 .times. 10.sup.3
20 [A-20]
HO.sub.3 SCH.sub.2 CH.sub.2
3 g
##STR77## 97 g 8.8 .times. 10.sup.3
21 [A-21]
##STR78## 4 g
##STR79## 97 g 7.5 .times. 10.sup.3
22 [A-22]
##STR80## 7 g
##STR81## 96 g 5.5 .times. 10.sup.3
23 [A-23]
##STR82## 6 g
##STR83## 94 g 4.5 .times. 10.sup.3
24 [A-24]
##STR84## 4 g
##STR85## 96 g 5.6 .times. 10.sup.3
__________________________________________________________________________
Synthetic Example 25 of Resin A: Resin A-25
A mixed solution of 100 g of 1-naphthyl methacrylate, 150 g of toluene and
50 g of isopropanol was heated at 80.degree. C. under a nitrogen stream.
5.0 g of 4,4'-azobis(4-cyano)valeic acid (hereinafter referred to as A. C.
V.) was then added thereto and stirred for 5 hours, 1 g of A. C. V. was
further added and stirred for 2 hours and then 1 g of A. C. V. was further
added and stirred for 3 hours. The thus resulting polymer has a weight
average molecular weight Mw of 7.5.times.10.sup.3.
##STR86##
Synthetic Example 26 of Resin A: Resin A-26
A mixed solution of 50 g of methyl methacrylate and 150 g of methylene
chloride was cooled at -20.degree. C. under a nitrogen stream, to which
1.0 g of a 10% hexane solution of 1,1-diphenylhexyllithium, prepared just
before it, was added, followed by stirring for 5 hours. Carbon dioxide was
introduced thereinto at a flow rate of 10 ml/cc while stirring for 10
minutes, cooling was then stopped and the reaction mixture was stirred and
allowed to stand until the temperature became room temperature. The
reaction mixture was reprecipitated in a solution of 1000 ml of methanol
in which 50 ml of 1N hydrochloric acid had been dissolved and a white
powder was collected by filtering. The thus resulting white powder was
washed with water and dried under reduced pressure, thus obtaining 18 g of
a polymer with M of 6.5.times.10.sup.3.
##STR87##
Synthetic Example 27 of Resin A: Resin A-27
A mixed solution of 95 g of n-butyl methacrylate, 4 g of thioglycolic acid
and 200 g of toluene was heated at a temperature of 75.degree. C. 1.0 g of
A. C. V. was added thereto and reacted for 6 hours and then 0.4 g of A. I.
B. N. was further added and reacted for 3 hours. The thus resulting
copolymer had Mw of 7.8.times.10.sup.3.
##STR88##
Preparation Example 1 of Macromonomer M: M-1
A mixed solution of 100 g of methyl methacrylate, 5 g of
.beta.-mercaptopropionic acid and 200 g of toluene was heated at a
temperature of 75.degree. C. while stirring under a nitrogen stream. 1.0 g
of A. I. B. N. was added thereto and reacted for 4 hours, 0.5 g of A. I.
B. N. was further added and reacted for 3 hours and then 0.3 g of A. I. B.
N. was further added and reacted for 3 hours. 8 g of glycidyl
methacrylate, 1.0 g of N,N-dimethyldodecylamine and 0.5 g of
t-butylhydroquinone were added to the reaction solution and stirred at a
temperature of 100.degree. C. for 12 hours. After cooling, this reaction
solution was subjected to reprecipitation in 200 ml of methanol to obtain
82 g of a white powder. The resulting powder had Mw of 7,800.
##STR89##
Preparation Example 2 of Macromonomer M: M-2
A mixed solution of 90 g of butyl methacrylate, 10 g of methacrylic acid, 9
g of thioethanol and 200 g of toluene was heated at a temperature of
70.degree. C. while stirring under a nitrogen stream. 1.0 g of A. I. B. N.
was added thereto and reacted for 4 hours, 0.5 g of A. I. B. N. was
further added and reacted for 3 hours and 0.3 g of A. I. B. N. was then
added and reacted for 3 hours. This reaction solution was cooled to room
temperature, to which 10 g of 2-carboxyethyl methacrylate was added and a
mixed solution of 17.2 g of dicyclohexylcarbodiimide (hereinafter referred
to as D. D. C.) and 50 g of methylene chloride was dropwise added for 1
hour. 1.0 g of t-butylhydroquinone was then added and stirred for 4 hours
as it was. The precipitated crystal was separated by filtration and the
resulting filtrate was subjected to reprecipitation in 2000 ml of
methanol. The precipitated oily product was collected by decantation,
dissolved in 150 ml of methylene chloride and reprecipitated again in 1000
ml of methanol. The oily product was collected and dried under reduced
pressure to obtain 54 g of a polymer with Mw of 5,800.
##STR90##
Preparation Example 3 of Macromonomer M: M-3
A mixed solution of 100 g of ethyl methacrylate, 150 g of tetrahydrofuran
and 50 g of isopropyl alcohol was heated at a temperature of 75.degree. C.
under a nitrogen stream. 4.0 g of A. C. V. was added thereto and reacted
for 5 hours and 1.0 g of A. C. V. was further added and reacted for 4
hours. After cooling, the reaction solution was subjected to
reprecipitation in 1500 ml of methanol and the oily product was collected
by decantation and dried under reduced pressure to obtain 85 g of a dried
product. To 50 g of the resulting dried product were added 15 g of
glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine and 1.0 g of
2,2'-methylenebis-(6-t-butyl-p-cresol) and stirred at a temperature of
100.degree. C. for 15 hours. After cooling, the reaction solution was
subjected to reprecipitation in 1000 ml of petroleum ether to obtain a
white power with Mw of 8,500.
##STR91##
Preparation Example 4 of Macromonomer M: M-4
A mixed solution of 50 g of the oligomer, obtained as an intermediate (oily
product collected and dried) in Preparation Example 3 of Macromonomer, 2.2
g of 2-hydroxyethyl methacrylate and 10 g of methylene chloride was
stirred at room temperature to which a mixed solution of 40 g of D.D.C.,
0.5 g of 3-dimethylaminopyridine and 35 g of methylene chloride was
dropwise added, and the mixture was stirred for 3 hours as it was. The
precipitated crystal was separated by filtration and the filtrate was
subjected to reprecipitation in 1000 ml of methanol two times. The
resulting powder was dried under reduced pressure to obtain a polymer with
Mw of 8,000.
##STR92##
Preparation Example 1 of Resin B: Resin B-1
A mixed solution of 80 g of ethyl methacrylate, 20 g of Macromonomer M-1
and 150 g of toluene was heated at a temperature of 75.degree. C. while
stirring under a nitrogen stream. 0.7 g of A. C. V. was added thereto and
reacted for 4 hours, 0.3 g of A. C. V. was further added and reacted for 2
hours and 0.3 g of A. C. V. was further added and reacted for 3 hours.
After cooling, the mixture was subjected to reprecipitation in 2000 ml of
methanol and filtered to obtain 76 g of a white powder with Mw of
9.8.times.10.sup.4.
##STR93##
Preparation Examples 2 to 12 or Resin B: Resins B-2 to B-12
Preparation Example 1 of Resin B-1 was repeated except using the compounds
shown in the following Table 4 instead of the methacrylate and
Macromonomer M-1, thus obtaining Resins B-2 to B-12 for dispersion
stabilization, having e,ovs/M/ w of 8.times.10.sup.4 to
1.2.times.10.sup.5.
TABLE 4
__________________________________________________________________________
##STR94##
Preparation x/y
Example of (weight
Resin B
Resin B
R.sub.44
ratio)
b.sub.5
b.sub.6
X.sub.3
__________________________________________________________________________
2 [B-2]
C.sub.2 H.sub.5
70/30 H CH.sub.3
COOCH.sub.3
3 [B-3]
C.sub.4 H.sub.9
60/40 H CH.sub.3
COOCH.sub.3
4 [B-4]
CH.sub.2 C.sub.6 H.sub.5
70/30 H CH.sub.3
COOC.sub.3 H.sub.7 (i)
5 [B-5]
C.sub.2 H.sub. 5
60/40 H CH.sub.3
COOC.sub.2 H.sub.5
6 [B-6]
CH.sub.3
70/30 H CH.sub.3
COOC.sub.4 H.sub.9
7 [B-7]
CH.sub.3
75/25 H H COOCH.sub.3
8 [B-8]
C.sub.2 H.sub.5
80/20 H H
##STR95##
9 [B-9]
C.sub.4 H.sub.9
85/15 H H CN
10 [B-10]
C.sub.6 H.sub.5
70/30 H CH.sub.3
COOC.sub.4 H.sub.9
11 [B-11]
C.sub.2 H.sub.5
80/20 CH.sub.3
H COOCH.sub.3
12 [B-12]
C.sub.2 H.sub.5
70/30 CH.sub.3
H COOC.sub.2 H.sub.5
__________________________________________________________________________
Preparation Example 13 of Resin B: Resin B-13
A mixed solution of 60 g of methyl methacrylate, 40 g of Macromonomer M-3,
0.8 g of thiomalic acid, 100 g of toluene and 50 g of isopropyl alcohol
was heated at 80.degree. C. while stirring under a nitrogen stream. 0.5 g
of 1,1'-azobis(cyclohexane-1-carbonamide) (hereinafter referred to as A.
B. C. C.) was added thereto and reacted for 4 hours, 0.3 g of A. B. C. C.
was further added and reacted for 3 hours and 0.3 g of A. B. C. C. was
further added and reacted for 4 hours. The reaction product was cooled,
then subjected to reprecipitation in 2000 ml of methanol, separated by
filtration and dried to obtain 78 g of a white powder with Mw of
8.6.times.10.sup.4.
##STR96##
Preparation Examples 14 to 22 of Resin B: Resins B-14 to B-22
Preparation Example 13 of Resin B-13 was repeated except using the
compounds shown in Table 5 in place of the methacrylate and macromonomer,
thus obtaining Resins B-14 to B-22 having Mw in the range of
8.times.10.sup.4 to 1.times.10.sup.5.
TABLE 5
__________________________________________________________________________
##STR97##
Preparation
Example of
Resin B
Resin B
W.sub.3 R.sub.45
X.sub.4 x.sub.1 /x.sub.2
R.sub.46
__________________________________________________________________________
14 [B-14]
HOOCCH.sub.2 C.sub.4 H.sub.9
-- 60/0/40
CH.sub.3
15 [B-15]
##STR98## C.sub.2 H.sub.5
-- 65/0/35
C.sub.2 H.sub.5
16 [B-16]
##STR99## C.sub.2 H.sub.5
##STR100## 50/20/30
C.sub.4 H.sub.9
17 [B-17]
##STR101## CH.sub.3
##STR102## 50/25/25
C.sub.2 H.sub.5
18 [B-18]
##STR103## CH.sub.3
##STR104## 40/10/50
C.sub.4 H.sub.9
19 [B-19]
##STR105## C.sub.4 H.sub.9
##STR106## 50/10/40
CH.sub.3
20 [B-20]
##STR107##
##STR108##
-- 60/0/40
CH.sub.2 C.sub.6
H.sub.5
21 [B-21]
##STR109## C.sub.4 H.sub.9
##STR110## 50/10/40
CH.sub.3
22 [B-22]
HO(CH.sub.2).sub.2
C.sub.2 H.sub.5
##STR111## 60/10/30
C.sub.2 H.sub.5
__________________________________________________________________________
Preparation Examples 23 to 28 of Resins B: Resins B-23 to B-28
Preparation Example 1 of Resin B was repeated except using the azobis
compounds shown in the following Table 6 in place of the polymerization
initiator, A. C. V., thus obtaining Resins B-23 to B-28 having Mw in the
range of 9.times.10.sup.4 to 1.5.times.10.sup.5.
TABLE 6
______________________________________
R.sub.47NNR.sub.47 : Azobis Compound
Preparation
Example of
Resin B Resin B Azobis Compound: R.sub.47
______________________________________
23 [B-23]
##STR112##
24 [B-24]
##STR113##
25 [B-25]
##STR114##
26 [B-26]
##STR115##
27 [B-27]
##STR116##
28 [B-28]
##STR117##
______________________________________
Preparation Example 29 of Resin B: Resin B-29
A mixed solution containing 90 g of methyl methacrylate, 10 g of
Macromonomer M-2 and 150 g of toluene was heated at a temperature of
75.degree. C. while stirring under a nitrogen stream. 0.6 g of A. B. C. C.
was added thereto and reacted for 4 hours, 0.4 g of A. B. C. C. was
further added and reacted for 3 hours and then 0.3 g of A. I. B. N. was
further added and reacted for 4 hours, followed by raising the temperature
to 90.degree. C. and reacting for 3 hours. After cooling, the reaction
product was subjected to reprecipitation in 2000 ml of methanol, the
precipitated viscous product was collected by decantation and dried under
reduced pressure, thus obtaining 76 g of a transparent and viscous product
with Mw of 1.1.times.10.sup.4.
##STR118##
Preparation Examples 30 to 39 of Resins B: Resins B-30 to B-39
Preparation Example 29 of Resin B was repeated except using the compounds
shown in the following Table 7 in place of the methacrylate and
macromonomer, thus obtaining Resins B-30 to B-39 having Mw in the range of
9.times.10.sup.4 to 1.2.times.10.sup.5.
TABLE 7
##STR119##
Preparation Example of Resin B Resin B R.sub.48 X.sub.5 x.sub.1
/x.sub.2 /y R.sub.49 Y.sub.8 r.sub.1
/r.sub.2 30 [B-30] C.sub.3 H.sub.7
-- 85/0/15 CH.sub.3
##STR120##
90/10 31 [B-31] C.sub.2 H.sub.5 -- 80/0/20 C.sub.4
H.sub.9
##STR121##
95/5 32 [B-32] C.sub.2
H.sub.5
##STR122##
59/1/40 C.sub.2 H.sub.5 -- 100/0 33 [B-33] C.sub.2
H.sub.5
##STR123##
68.5/1.5/30 CH.sub.2 C.sub.6 H.sub.5 -- 100/0 34 [B-34] CH.sub.2
C.sub.6 H.sub.5 -- 80/0/20 C.sub.4
H.sub.9
##STR124##
90/10 35 [B-35] C.sub.3
H.sub.7
##STR125##
69.2/0.8/30 C.sub.2
H.sub.5
##STR126##
80/20 36 [B-36] C.sub.6
H.sub.5
##STR127##
80/10/10 C.sub.2
H.sub.5
##STR128##
95/5 37 [B-37] C.sub.2
H.sub.5
##STR129##
72/8/20
##STR130##
##STR131##
85/15 38 [B-38] C.sub.2 H.sub.5 -- 75/0/25 C.sub.2
H.sub.5
##STR132##
90/10 39 [B-39] CH.sub.2 C.sub.6 H.sub.5 -- 85/0/15 C.sub.6 H.sub.5
##STR133##
95/5
Example 1
A mixture of 6 g (as solid content) of Resin A-1 prepared in Preparation
Example 1 of Resin A, 34 g (as solid content) of Resin B-1 prepared in
Preparation Example 1 of Resin B, 4 g (as solid content) of Hydrophilic
Resin Grains prepared in Preparation Example 2 of Resin Grains, 200 g of
zinc oxide, 0.018 g of a cyanine dye (A) having the following structure,
0.40 g of tetrahydrophthalic anhydride and 300 g of toluene was ball
milled for 2 hours. The thus resulting light-sensitive layer forming
dispersion was applied to a paper rendered electrically conductive to give
a dry coverage of 22 g/m.sup.2 by a wire bar coater, followed by drying at
110.degree. C. for 20 seconds. The thus coated paper was allowed to stand
in a dark place at a temperature of 20.degree. C. and a relative humidity
of 65% for 24 hours to prepare an electrophotographic light-sensitive
material.
##STR134##
Example 2
Example 1 was repeated except using 34 g of Resin B-29 in place of 34 g of
Resin B-1, thus preparing an electrophotographic light-sensitive material.
Comparative Example 1
Example 1 was repeated except using 40 g of only Resin D having the
following structure as the binder resin, thus preparing an
electrophotographic light-sensitive material D.
##STR135##
These light-sensitive material were then subjected to evaluation of the
film property (surface smoothness), film strength electrostatic
characteristics and reproduced image quality, in particular, under ambient
conditions of 30.degree. C. and 80% RH. Furthermore, when using these
light-sensitive materials as a master plate for offset printing, the
oil-desensitivity of the photoconductive layer in terms of a contact angle
of the photoconductive layer with water after oil-desensitization and the
printing performance in terms of a stain resistance and printing
durability.
The results are shown in Table 8.
TABLE 8
______________________________________
Comparative
Example 1
Example 2 Example 1
______________________________________
Smoothness of
110 105 80
Photoconductive
Layer.sup.1)
Strength of Photo-
94 93 68
conductive Layer.sup.2)
Electrostatic
Characteristics.sup.3)
V.sub.10 /(-V)
I (20.degree. C., 65% RH)
575 570 445
II (30.degree. C., 80% RH)
560 550 220
D. R. R. (%)
I 82 80 40
II 78 76 10
E.sub.1/10 (erg/m.sup.2)
I 18 20 120
II 15 17 no photo-
conductivity
Image Quality.sup.4)
I good good disappearance
of fine lines
and letter, D.M.
does not appear.
II good good no discrimina-
tion of image
Contact Angle with
less than less than 10-20.degree.
Water.sup.5) (degrees)
10.degree.
10.degree.
large
dispersion
Printing no stain no stain background
Durability.sup.6)
even after
even after
staining from
10000 prints
10000 prints
printing start
______________________________________
The characteristic items described in Table 8 are evaluated as follows:
1) Smoothness of Photoconductive layer
The resulting light-sensitive material was subjected to measurement of its
smoothness (sec/cc) under an air volume of 1 cc using a Bekk smoothness
tester (manufactured by Kumagaya Riko KK).
2) Mechanical Strength of Photoconductive Layer
The mechanical strength is defined as a film retention ratio (%) obtained
by rubbing the surface of the resulting light-sensitive material
repeatedly 1000 times with an emery paper (No. 1000) under a load of 55
g/cm.sup.2 using a surface property tester of Heidon-14 type (-commercial
name-, manufactured by Shinto Kagaku KK) and removing the worn-off powder
to give a weight decrease of the light-sensitive layer.
3) Electrostatic Characteristics
Each of the light-sensitive materials was subjected to corona discharge at
a voltage of 6 kV for 20 seconds in a dark room at a temperature of 20
.degree. C. and relative humidity of 65% using a paper analyzer (Paper
Analyzer Sp-428 -commercial name- manufactured by Kawaguchi Denki KK) and
after allowed to stand for 10 seconds, the surface potential V.sub.10 was
measured. Then, the sample was further allowed to stand in the dark room
as it was for 90 seconds to measure the surface potential V.sub.100, thus
obtaining the retention of potential after the dark decay for 60 seconds,
i.e., dark decay retention ratio (DRR (%)) represented by (V.sub.90
/V.sub.10).times.100 (%). Moreover, the surface of the photoconductive
layer was negatively charged to -400 V by corona discharge, then
irradiated with monochromatic light of a wavelength of 780 nm and the time
required for dark decay of the surface potential (V.sub.10) to 1/10 was
measured to evaluate an exposure quantity E.sub.1/10 (erg/cm.sup.2). The
ambient conditions for the measurement of the electrostatic
characteristics were:
I . . . 20.degree. C., 65% RH
II . . . 30.degree. C., 85% RH
4) Image quality
Each of the light-sensitive materials was allowed to stand for a whole day
and night under the following ambient conditions, charged at -5 KV,
imagewise exposed rapidly at a pitch of 25 .mu.m and a scanning speed of
300 m/sec under irradiation of 64 erg/cm.sup.2 on the surface of the
light-sensitive material using a gallium-aluminum-arsenic semiconductor
laser (oscillation wavelength: 780 nm) with an output of 2.8 mW as a light
source, developed with a liquid developer, ELP-T (-commercial name-,
manufactured by Fuji Photo Film Co., Ltd.) and fixed to obtain a
reproduced image which was then subjected to visual evaluation of the fog
and image quality:
I . . . 20.degree. C., 65% RH
II . . . 30.degree. C., 85% RH
5) Contact Angle with Water
Each of the light-sensitive materials was passed once through an etching
processor using an oil-desensitizing solution ELP-EX (-commercial name-,
made by Fuji Photo Film Co., Ltd.) to render the surface of the
photoconductive layer oil-desensitized. On the thus oil-desensitized
surface was placed a drop of 2 .mu.l of distilled water and the contact
angle formed between the surface and water was measured by a goniometer.
6) Printing Durability
Each of the light-sensitive materials was subjected to printing plate
making under the same conditions as the above described item 4) to form a
toner image and then to oil-desensitization under the same conditions as
in the above described item 5). The resulting printing plate was mounted,
as an offset master, on an offset printing machine (Oliver 52 type
-commercial name- manufactured by Sakurai Seisakujo KK) to obtain the
printing durability which was defined by the number of prints which could
be obtained without forming background stains on the non-image areas of
the print and meeting with any problem on the image quality of the image
areas by printing. The more the prints, the better the printing
durability.
As can be seen from Table 8, in Comparative Example 1 using the prior art
resin, the photoconductive layer showed much worse surface smoothness and
electrostatic characteristics and when using as an offset master,
background stains markedly occurred from the beginning in the print and
the contact angle with water was larger, i.e. 20.degree. or more in spite
of using the hydrophilic resin grains of the present invention. This is
probably due to that interaction of the binder resin with photoconductive
zinc oxide is not suitable and aggregation or strong adsorption of the
binder resin on zinc oxide grains proceeds so that the oil-desensitization
by the oil-desensitizing solution is uneven or insufficient in spite of
adding the hydrophilic resin grains according to the present invention.
The light-sensitive material of the present invention, as in Example 1 and
Example 2, is excellent in smoothness, film strength and electrostatic
characteristics of the photoconductive layer and the contact angle with
water after the oil-desensitizing treatment when used as an offset master
is small, i.e. at most 10.degree.. Thus, it was found by observation of
real prints that it could form a clear image and produced more than 10,000
prints without background stains.
Examples 3 to 9
Example 1 was repeated except using 6 g of each of Resins A shown in the
following Table 9, 34 g of each of Resins B shown in Table 9 and 4 g of
the hydrophilic resin grains instead of 6 g of Resin A-1, 34 g of Resin
B-4 and 4 g of the hydrophilic resin grains and using 0.020 g of a methine
dye (B) having the following structure instead of 0.018 g of the cyanine
dye (A), thus obtaining light-sensitive materials.
##STR136##
TABLE 9
__________________________________________________________________________
Hydrophilic
Strength
Electrostatic Image
Resin of Photo-
Characteristics (30.degree. C., 80%
Quality Printing
Example
Resin A
Resin B
Grains conductivity
V.sub.10
D.R.R.
E.sub.1/10 (erg/cm.sup.2)
(30.degree. C., 80%
Durability
__________________________________________________________________________
3 [A-1] [B-2]
1 95 -555 78 20 .largecircle.
more than
good 10,000
4 [A-3] [B-3]
3 93 -550 80 18 .largecircle.
more than
10,000
5 [A-5] [B-4]
4 94 -575 83 18 .largecircle.
more than
10,000
6 [A-8] [B-10]
9 93 -560 79 21 .largecircle.
more than
10,000
7 [A-18]
[B-11]
15 95 -565 81 20 .largecircle.
more than
10,000
8 [A-19]
[B-13]
2 96 -575 83 20 .largecircle.
more than
10,000
9 [A-21]
[B-31]
6 94 -570 81 19 .largecircle.
more than
10,000
__________________________________________________________________________
Each of the light-sensitive material of Examples 3 to 9 exhibited excellent
electrostatic characteristics, dark decay retention and photosensitivity
and gave a clear reproduced image that is free from occurrence of
background stains and disappearance of fine lines even under severer
conditions, e.g., high temperature and high humidity (30.degree. C., 80%
RH). When printing was carried out using as an offset master plate, 10,000
or more prints of clear image were obtained without background stains.
Example 10
A mixture of 6.5 g (as solid content) of Resin A-25, 33.5 g (as solid
content) of Resin B-15, 3.5 g of Hydrophilic Resin Grains prepared in
Preparation Example 3 of Resin Grains, 200 g of photoconductive zinc
oxide, 0.50 g of Rose Bengal, 0.25 g of bromophenol blue, 0.30 g of
uranine, 0.40 g of phthalic anhydride and 240 g of toluene was ball milled
for 4 hours. The thus resulting light-sensitive layer forming dispersion
was applied to a paper rendered electrically conductive to give a dry
coverage of 18 g/m.sup.2 by a wire bar coater, followed by heating at
110.degree. C. for 30 seconds and at 120.degree. C. for 2 hours. Then, the
coated paper was allowed to stand for 24 hours under conditions of
20.degree. C. and 65% RH to prepare an electrophotographic light-sensitive
material.
The resulting light-sensitive material was then subjected to evaluation of
various characteristics in an analogous manner to Example 1, thus
obtaining a surface smoothness of the photoconductive layer of 120 sec/cc,
V.sub.10 of -560 V, D.R.R. of 93% and E.sub.1/10 of 10.3 lux.multidot.sec.
When printing was carried out using as an offset master plate, at least
10,000 prints of clear image were obtained without background stains.
Measurement of the electrostatic characteristics and image quality was
carried out as follows:
Electrostatic Characteristics
Each of the light-sensitive materials was subjected to corona discharge at
a voltage of 6 kV for 20 seconds in a dark room at a temperature of 20
.degree. C. and relative humidity of 65% using a paper analyzer (Paper
Analyzer Sp-428 -commercial name- manufacture by Kawaguchi Denki KK) and
after allowed to stand for 10 seconds, the surface potential V.sub.10 was
measured. Then, the sample was further allowed to stand in the dark room
as it was for 60 seconds to measure the surface potential V.sub.70, thus
obtaining the retention of potential after the dark decay for 60 seconds,
i.e., dark decay retention ratio (DRR (%)) represented by (V.sub.70
/V.sub.10).times.100 (%). Moreover, the surface of the photoconductive
layer was negatively charged to -400 V by corona discharge, then
irradiated with visible ray at an illumination of 2.0 lux and the time
required for dark decay of the surface potential (V.sub.10) to 1/10 was
measured to evaluate an exposure quantity E.sub.1/10 (lux.multidot.sec).
Image quality
Each of the light-sensitive materials was allowed to stand for a whole day
and night under the following ambient conditions and a reproduced image
was formed thereon using an automatic printing plate making machine
ELP-404 V (-commercial name-, made by Fuji Photo Film Co., Ltd., Ltd.) and
ELP-T as a toner to visually evaluate the fog and image quality: (I)
20.degree. C., 65% RH and (II) 30.degree. C., 80% RH.
Examples 11 to 22
Example 1 was repeated except using 6.0 g (as solid content) of each of
Resins A, 34.0 g (as solid content) of each of Resins B and 4 g (as solid
content) of each of Hydrophilic Resin Grains, as shown in Table 10, and
0.20 g of a cyanine dye having the following structure to prepare a
light-sensitive material:
##STR137##
TABLE 10
______________________________________
Hydrophilic
Example Resin A Resin B Resin Grains
______________________________________
11 [A-20] [B-5] 1
12 [A-21] [B-6] 2
13 [A-22] [B-7] 6
14 [A-23] [B-8] 7
15 [A-24] [B-9] 8
16 [A-9] [B-13] 10
17 [A-10] [B-15] 12
18 [A-11] [B-16] 13
19 [A-16] [B-17] 14
20 [A-17] [B-19] 15
21 [A-18] [B-20] 16
22 [A-19] [B-21] 3
______________________________________
Each of the light-sensitive materials prepared in Examples 11 to 22 was
subjected measurement of the electrostatic characteristics and printing
property in an analogous manner to Example 1, thus exhibiting excellent
electrostatic characteristics, dark decay retention and photosensitivity
and giving a clear reproduced image that is free from occurrence of
background stains and disappearance of fine lines even under severer
conditions, e.g., high temperature and high humidity (30.degree. C., 80%
RH). When printing was carried out using as an offset master plate, 10,000
or more prints of clear image were obtained without background stains on a
non-image area.
Examples 23 to 30
Example 10 was repeated except using 6.5 g (as solid content) of each of
Resins A and 33.5 g (as solid content) of each of Resins B as shown in the
following Table 11 instead of 6.5 g of Resin A-25 and 33.5 g of Resin B-15
in Example 10, thus obtaining a light-sensitive material.
TABLE 11
______________________________________
Example Resin A Resin B
______________________________________
23 [A-2] [B-1]
24 [A-7] [B-4]
25 [A-8] [B-15]
26 [A-13] [B-29]
27 [A-14] [B-32]
28 [A-15] [B-33]
29 [A-26] [B-35]
30 [A-27] [B-36]
______________________________________
Each of the light-sensitive materials prepared in Examples 23 to 30 was
subjected to plate making using ELP-404V to obtain a clear reproduced
image. When printing was carried out using as an offset master plate,
10,000 or more prints of clear image were obtained without background
stains.
According to the present invention, there can be provided a lithographic
printing plate precursor having a very excellent printing property.
Furthermore, the present invention can provide a lithographic printing
plate, whereby the hydrophilic resin grains do not cause background stains
of a non-image area and a large number of prints can be obtained In
addition, the electrophotographic lithographic printing precursor can
exhibit very excellent electrostatic characteristics in spite of that a
spectral sensitizing dye completely differ in chemical structure and in
particular, can give a very excellent reproduced image in the scanning
exposure system by a semiconductor laser.
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